U.S. patent application number 12/084233 was filed with the patent office on 2009-07-02 for solid crop protection agents containing polyalkoxylate, method for their production and use thereof.
This patent application is currently assigned to BASF SE. Invention is credited to Thomas Christen, Karl-Friedrich Jager, Reiner Kober, Michael Krapp, Reinhold Stadler, Karl-Otto Westphalen.
Application Number | 20090170704 12/084233 |
Document ID | / |
Family ID | 37649532 |
Filed Date | 2009-07-02 |
United States Patent
Application |
20090170704 |
Kind Code |
A1 |
Kober; Reiner ; et
al. |
July 2, 2009 |
Solid Crop Protection Agents Containing Polyalkoxylate, Method for
Their Production and Use Thereof
Abstract
The invention relates to solid plant protection compositions
comprising: a) liquid or low melting point polyalkoxylate; and b) a
carrier based on relatively high molecular weight sulfonate,
wherein (i) the weight ratio of liquid or low melting point
polyalkoxylate to plant protection active agent is at least 1:2;
(ii) the proportion of liquid or low melting point polyalkoxylate,
based on the total weight of the relatively high molecular weight
sulfonates, is at least 30% by weight; and (iii) the weight ratio
of liquid or low melting point polyalkoxylate to relatively high
molecular weight sulfonate is at most 3:1. The invention also
relates to processes for their preparation and the use of the plant
protection compositions for the treatment of plants and their
habitat as well as corresponding processes, and also spray mixtures
comprising such a plant protection composition.
Inventors: |
Kober; Reiner; (Fussgonheim,
DE) ; Stadler; Reinhold; (Kirrweiler, DE) ;
Westphalen; Karl-Otto; (Speyer, DE) ; Christen;
Thomas; (Dannstadt, DE) ; Krapp; Michael;
(Altrip, DE) ; Jager; Karl-Friedrich;
(Limburgerhof, DE) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Assignee: |
BASF SE
LUDWIGSHAFEN
DE
|
Family ID: |
37649532 |
Appl. No.: |
12/084233 |
Filed: |
October 27, 2006 |
PCT Filed: |
October 27, 2006 |
PCT NO: |
PCT/EP2006/067899 |
371 Date: |
April 28, 2008 |
Current U.S.
Class: |
504/360 ;
514/383; 514/772.3; 514/772.4 |
Current CPC
Class: |
A01N 25/30 20130101;
A01N 43/653 20130101; A01N 43/653 20130101; A01N 25/04 20130101;
A01N 25/30 20130101; A01N 43/653 20130101; A01N 2300/00
20130101 |
Class at
Publication: |
504/360 ;
514/772.3; 514/383; 514/772.4 |
International
Class: |
A01N 25/10 20060101
A01N025/10; A01N 43/653 20060101 A01N043/653; A01P 3/00 20060101
A01P003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 28, 2005 |
DE |
10 2005 051 823.0 |
Claims
1-50. (canceled)
51. A solid plant protection composition comprising: a) liquid or
low melting point polyalkoxylate; and b) a carrier based on
relatively high molecular weight sulfonate, wherein i) the weight
ratio of liquid or low melting point polyalkoxylate to plant
protection active agent is at least 1:2 and the proportion of
liquid or low melting point polyalkoxylate, based on the total
weight of the composition, is at least 15% by weight; ii) the
proportion of liquid or low melting point polyalkoxylate, based on
the total weight of the relatively high molecular weight
sulfonates, is at least 30% by weight; and iii) the weight ratio of
liquid or low melting point polyalkoxylate to relatively high
molecular weight sulfonate is at most 3:1.
52. The composition according to claim 51, comprising from 1 to 50%
by weight, preferably from 2 to 40% by weight and in particular
from 2.5 to 35% by weight of plant protection active agent.
53. The composition according to claim 51, wherein the plant
protection active agent is chosen from fungicidal active agents
from the triazoles series, in particular epoxiconazole,
metconazole, tebuconazole, flusilazole, fluquinconazole,
triticonazole, propiconazole, penconazole, cyproconazole and
prothioconazole, in addition from fungicidal active agents from the
strobilurins series, in particular azoxystrobin, pyraclostrobin,
dimoxystrobin, trifloxystrobin, fluoxastrobin, picoxystrobin and
orysastrobin, and also prochloraz, iprodione, dimethomorph and
pyrimethanil.
54. The composition according to claim 51, wherein the
polyalkoxylate is chosen from optionally end-group-modified
alkoxylated fatty alcohols, alkoxylated fatty acid esters,
alkoxylated fatty amines, alkoxylated glycerides, alkoxylated
sorbitan esters, alkoxylated alkylphenols and alkoxylated di- and
tristyrylphenols with alkoxylate moieties.
55. The composition according to claim 51, wherein the
polyalkoxylate is chosen from alcohol polyalkoxylates of the
formula (I)
R.sup.7--O--(C.sub.mH.sub.2mO).sub.x--(C.sub.nH.sub.2nO).sub.y--(C.sub.pH-
.sub.2pO).sub.z--R.sup.6 (I) in which R.sup.6 is an organic
radical; R.sup.7 is an aliphatic hydrocarbon radical with from 3 to
100 carbon atoms; m, n and p are, independently of one another, a
whole number from 2 to 6, preferably 2, 3, 4 or 5; x, y and z are,
independently of one another, a number from 0 to 1000; and x+y+z
corresponds to a value from 2 to 1000.
56. The composition according to claim 55, wherein R.sup.7 is
branched or linear C.sub.3-30-alkyl, preferably C.sub.5-24-alkyl,
or C.sub.3-30-alkenyl, preferably C.sub.5-C.sub.24-alkenyl.
57. The composition according to claim 51, comprising at least 20%
by weight, preferably at least 25% by weight and in particular at
least 30% by weight of alkoxylate.
58. The composition according to claim 51, comprising at most 70%
by weight, preferably at most 60% by weight and in particular at
most 45% by weight of alkoxylate.
59. The composition according to claim 51, wherein the relatively
high molecular weight sulfonate exhibits a weight-average molecular
weight of at least 1 kDa, preferably of at least 2.5 kDa and in
particular of at least 5 kDa.
60. The composition according to claim 51, wherein the relatively
high molecular weight sulfonate is a lignosulfonate.
61. The composition according to claim 51, wherein the relatively
high molecular weight sulfonate is a condensation product based on
a sulfonated aromatic compound, an aldehyde and/or ketone and, if
appropriate, on a compound chosen from nonsulfonated aromatic
compounds, urea and urea derivatives.
62. The composition according to claim 61, wherein the condensation
product comprises repeat units with the structure of the formula
(IIa) ##STR00011## and/or formula (IIb) ##STR00012## and/or formula
(IIc) ##STR00013## in which R.sup.8 is hydrogen, one or more
hydroxyl groups or one or more C.sub.1-8-alkyl radicals; q1
corresponds to a value from 100 to 10.sup.10; and A is methylene,
1,1-ethylene or a group of the formulae ##STR00014##
63. The composition according to claim 61, wherein the condensation
product comprises repeat units with the structure of the formula
(III): ##STR00015## in which R.sup.9 is hydrogen, one or more
hydroxyl groups or one or more C.sub.1-8-alkyl radicals; q2
corresponds to a value from 100 to 10.sup.10; A is methylene,
1,1-ethylene or a group of the formulae ##STR00016##
64. The composition according to claim 51, wherein the relatively
high molecular weight sulfonate is a copolymer, the constituent
monomers M of which comprise .alpha.) at least one
monoethylenically unsaturated monomer M1 exhibiting at least one
sulfonic acid group, and .beta.) at least one neutral
monoethylenically unsaturated monomer M2.
65. The composition according to claim 51, wherein the sulfonate is
an ammonium, alkali metal, alkaline earth metal or transition metal
sulfonate.
66. The composition according to claim 51, comprising at least 15%
by weight, preferably at least 25% by weight and in particular at
least 30% by weight of relatively high molecular weight
sulfonate.
67. The composition according to claim 51, comprising at most 80%
by weight, preferably at most 70% by weight and in particular at
most 55% by weight of relatively high molecular weight
sulfonate.
68. The composition according to claim 51 wherein the weight ratio
of liquid or low melting point polyalkoxylate to relatively high
molecular weight sulfonate is at most 2:1.
69. The composition according to claim 51, wherein the weight ratio
of liquid or low melting point polyalkoxylate to relatively high
molecular weight sulfonate is at least 3:10.
70. The composition according to claim 51, wherein the component
(b) comprises b1) relatively high molecular weight sulfonate; and
b2) inorganic solid.
71. The composition according to claim 20, wherein the inorganic
solid is sparingly soluble or insoluble in water.
72. The composition according to claim 70, wherein the inorganic
solid is chosen from substances based on aluminum oxide, in
particular aluminum oxide and bauxite, and substances based on
silicon dioxide, in particular silicates and silicate minerals,
above all diatomaceous earths (kieselguhr, diatomite), silicas,
pyrophylite, talc, mica and clays, such as kaolinite, bentonite,
montmorillonite and attapulgite.
73. The composition according to claim 72, the proportion of
inorganic solid therein altogether being less than 15% by weight,
in particular less than 10% by weight and particularly preferably
less than 5% by weight.
74. The composition according to claim 70, wherein the weight ratio
of relatively high molecular weight sulfonate to inorganic solid is
at least 2, preferably at least 5 and in particular at least
10.
75. The composition according to claim 51, furthermore comprising:
c) additional auxiliary.
76. The composition according to claim 75, wherein the additional
auxiliary is chosen from c1) surface-active auxiliaries; c2)
suspension agents, antifoaming agents, retention agents, pH
buffers, drift retardants and other auxiliaries for improving the
handleability and/or physical properties of the formulation; c3)
chelating agents.
77. The composition according to claim 75, comprising at most 60%
by weight, preferably at most 55% by weight and in particular at
most 50% by weight of additional auxiliary.
78. The composition according to claim 51, furthermore comprising:
d) water-soluble inorganic salt.
79. The composition according to claim 78, wherein the inorganic
salt is ammonium sulfate.
80. The composition according to claim 51, which is essentially
anhydrous.
81. The composition according to claim 51, to be exact a
granule.
82. The composition according to claim 81, the granule being a
water-dispersible granule (WG) or water-soluble granule (SG).
83. The composition according to claim 81, the granule being a
fluidized-bed granule (FBG).
84. The composition according to claim 51, to be exact a
powder.
85. The composition according to claim 84, the powder being a dry
flowable powder (DF).
86. A process for the preparation of a composition according to
claim 51, wherein fluid is removed from a fluid-comprising mixture
comprising at least a portion of the ingredients and the solid is
obtained at least partially freed from the fluid.
87. The process according to claim 86, wherein the fluid is
water.
88. The process according to claim 86, wherein the fluid is removed
by freeze drying or spray drying.
89. The process according to claim 86, wherein the fluid is removed
in the fluidized bed process.
90. The process according to claim 86, wherein fluid is removed
from a fluid-comprising mixture comprising component (a), (b) and
plant protection active agent.
91. The process according to claim 86, wherein a solid comprising
components (a) and (b) is introduced, a fluid-comprising mixture
comprising plant protection active agent is added and fluid is
removed.
92. The process according to claim 91, wherein the fluid-comprising
mixture is a concentrate comprising at least 5% by weight of plant
protection active agent.
93. The process according to claim 86, wherein a solid comprising
plant protection active agent is introduced, a fluid-comprising
mixture comprising components (a) and (b) is added and fluid is
removed.
94. A process of for the preparation of a solution, dispersion or
emulsion (spray mixture) for the fungicidal, insecticidal or
herbicidal treatment of plants and/or their habitat which comprises
dissolving, dispersing or emulsifying a solid plant protection
composition according to claim 51 in water.
95. A process for the fungicidal, insecticidal or herbicidal
treatment of plants and their habitat, wherein a solid plant
protection composition according to claim 51 is dissolved,
dispersed or emulsified and plants and/or their habitat are treated
with the resulting solution, dispersion or emulsion (spray
mixture).
96. The process according to claim 95, wherein the dissolving,
dispersing or emulsifying is carried out in the tank mix
method.
97. The process according to claim 95, wherein the treatment is
carried out in the spray method.
98. A spray mixture, comprising a plant protection composition
according to claim 51.
99. The spray mixture according to claim 98, comprising from 0.0001
to 10% by weight, preferably from 0.001 to 1% by weight and in
particular from 0.01 to 0.5% by weight of plant protection active
agent.
100. A solid plant protection composition comprising: a) liquid or
low melting point polyalkoxylate, the low melting point
polyalkoxylate having a melting point of less than 40.degree. C. at
standard pressure; and b) a carrier based on relatively high
molecular weight sulfonate, wherein i) the weight ratio of liquid
or low melting point polyalkoxylate to plant protection active
agent is at least 1:2; ii) the proportion of liquid or low melting
point polyalkoxylate, based on the total weight of the relatively
high molecular weight sulfonates, is at least 30% by weight; iii)
the weight ratio of liquid or low melting point polyalkoxylate to
relatively high molecular weight sulfonate is at most 3:1; and iv)
the composition comprises a total of 0 to 15% by weight of
substances based on aluminum oxide and/or on silicon dioxide.
Description
[0001] The invention relates to solid plant protection compositions
with liquid or low melting point polyalkoxylates, processes for
their preparation and the use of the plant protection compositions
for the treatment of plants and their habitat as well as
corresponding processes, and also spray mixtures comprising such a
plant protection composition.
[0002] Year in, year out, worldwide, a considerable portion of
agricultural production is destroyed by plant pests in the broadest
sense. Plant pests can not only lead to crop failure on a large
scale, which threatens human alimentation, but also destroy the
vegetative parts of useful perennial plants and thereby impair
agriculturally productive land and whole ecosystems with lasting
effect.
[0003] Plant pests belong to different groups of organisms.
Numerous important pests are to be found among higher animals, in
particular among insects and acarids, and furthermore among
nematodes and snails; vertebrates, such as mammals and birds, are
today of lesser importance in industrialized countries. Numerous
groups of microbes, including fungi, bacteria inclusive of
mycoplasmas, viruses and viroids, can cause crop failure and loss
of value; even products still essentially edible are often no
longer marketable for aesthetic reasons. Finally, weeds which
compete with useful plants for limited living space and other
resources also belong to pests in the broad sense.
[0004] Parasitic fungi are particularly important as pests. Mildew
is to be feared in horticulture, ergot (Claviceps) is a danger to
man and animals due to its toxic alkaloids, and the damage to
European potato stocks by Phytophthora infestans in the middle of
the 19th century, which led to famine and political unrest,
achieved historical importance.
[0005] The generic term "plant protection compositions" brings
together substances and mixtures of substances which can be used
for specific control of plant pests. They can be classified
according to target organisms (insecticides, fungicides,
herbicides, and the like), according to manner of action (stomach
poison, contact poisons, repellents, and the like) or according to
chemical structure. Due to the resistance of fungal spores and the
lack of natural enemies, chemical control is the only effective
measure in particular against phytotoxic fungi, care having to be
taken to locally maximize the effect of the fungicides in order not
to damage symbiotic fungi (mycorrhizal fungi) in other places.
[0006] Plant protection compositions can be pure substances;
however, compositions are in many cases advantageous. Such
compositions can, in addition to the substance or substances having
an immediate effect on the pests (subsequently denoted as plant
protection active agent), comprise various types of accompanying
and auxiliary substances which in various ways can strengthen the
desired effect (in the literature then generally known as
"additives", "adjuvants", "accelerators", "boosters" or
"enhancers"), simplify the handling, increase the shelf life or
otherwise improve the properties of the product. Subsequently, a
plant protection composition always describes a combination of one
or more plant protection active agents and one or more
auxiliaries.
[0007] Typically, plant protection compositions are dissolved,
emulsified or dispersed in aqueous medium in order thus to obtain
the aqueous spray mixture described as "tank mix" which is then
applied in the "spray method" to the plants or their habitat. The
accompanying and auxiliary substances must be appropriately chosen
in order to obtain a suitable tank mix.
[0008] The action of the effect-promoting additives is generally
based on their surface activity with regard to the hydrophobic
plant surface, which improves the contact of the spray mixture with
the plant surface. A distinction is made in detail between wetters,
spreaders and penetrators, these groups naturally overlapping.
Subsequently, the general term "additive" is used without
consideration of physical details to describe auxiliaries for
enhancing the effect of agrotechnical active agents, in particular
plant protection agents.
[0009] Nonionic hydrophobic alkoxylates are known as suitable
additives for various plant protection active agents, in particular
fungicides.
[0010] Such alkoxylates are above all used in liquid formulations,
including solutions, emulsions, suspensions, suspoemulsions and
other forms. For example, relatively stable suspoemulsions are
represented in EP 707 445 B1.
[0011] However, liquid plant protection compositions exhibit a
number of disadvantages: on application, the danger arises of
runoff and seepage into the soil. Storage and transportation are
more expensive since the solvent has to be transported or stored
too and receptacles for liquid plant protection compositions, for
example containers or cans, cause waste disposal problems since
simple incineration is generally impossible. The stability of
liquid plant protection compositions with regard to heat, cold and
shear forces and accordingly their storage stability is low and
requires expensive emulsifying and stabilizing additives. Moreover,
many active agents or active agent combinations can only with
difficulty be formulated in liquid form since they are prone to
crystallization and/or demixing. The solvents as such are often
readily flammable, are skin irritating or have an unpleasant smell;
if water is used as solvent, the problem of hydrolytic
decomposition of active agent frequently occurs during prolonged
storage.
[0012] Solid plant protection compositions, in particular those
based on dust-free solid granules, offer considerable advantages in
comparison with liquid plant protection compositions, which affects
use, storage, transportation, stability and waste disposal of
packaging materials. However, the low melting point of the
abovementioned alkoxylates, which leads to problems on
incorporation in solid plant protection compositions, is frequently
disadvantageous. Thus, conventional solid plant protection
compositions can only include small amounts of liquid, oily or low
melting point additives, such as those represented by the
alkoxylates, since otherwise agglutination and aggregation of the
granules occur. Typically, less than 15% by weight merely of such
additives can be added without harming the storage stability.
[0013] The usable proportion of additives can conventionally be
increased by use of sorbent materials, also known as carriers,
based on inorganic compounds, especially based on silicate. By
binding the additives, they improve the mechanical properties of
the composition and prevent aggregation of the granules during
storage. However, inorganic sorbent materials have a tendency to
form very fine-grained powders and dusts, which again raises
problems in the preparation and processing and in particular
necessitates expensive safety engineering, especially in the area
of respiratory protection. The health hazard from fine-grained
inorganic dusts is known. In addition, the solid constituents can
also exhibit undesirable effects after application.
[0014] U.S. Pat. No. 6,239,115 B1 discloses granules with the
active agent polyoxin and naphthalenesulfonic acid-formaldehyde
condensates as dispersant. Typically, however, only 2% of
polyoxyethylene alkyl ethers were incorporated in the granules
here.
[0015] DE 102 17 201 discloses low-dust granules with up to 9% of
alkylsulfonates and/or polyglycols. The polyglycols are generally
not suitable enhancers of activity since they are purely
water-soluble and are not surface-active.
[0016] GB 1 291 251 discloses granules with merely up to 5% of
anionic and nonionic surfactants but up to 50% of calcium
lignosulfonates.
[0017] The incorporation of surface-active and activity-enhancing
auxiliaries can, e.g., also be carried out via melt extrudates
(melt extrusion process). Examples thereof are found in WO
93/25074, where virtually without exception carbowax (PEG 8000) is
used as "binder". PEGs, i.e. polyethylene glycols, are generally
very hydrophilic and thus very highly soluble in water.
[0018] EP 843 964 B1 discloses essentially extrusion granules with
up to 10% of tristyryl-phenyl polyethoxylates, inorganic carrier
systems as in U.S. Pat. No. 6,416,775 B1 being used. Thus,
diatomaceous earths (kieselguhr), in particular Celite products,
are used in U.S. Pat. No. 6,416,775 B1 or in U.S. Pat. No.
6,375,969 B1 as sorbent agents.
[0019] Granules made of lignosulfonates with relatively low
proportions of di- and tristyrylphenol ethoxylates are disclosed in
DE 696 24 381 T2, WO 97/24173 or EP 880 402 B1.
[0020] A route to the preparation of granules with high contents of
liquid amphiphilic surface-active additives is disclosed, e.g., in
WO 99/56543 and WO 99/08518. "Clathrates" formed from urea
derivatives and polysiloxane-derived alcohol ethoxylates are
disclosed here. It is stated that powders or granules with up to
30% of surface-active auxiliaries can be prepared.
[0021] A solution for the preparation of herbicidal granules with
"active agents" is demonstrated in WO 93/05652. If fatty alcohol
ethoxylates are used, high proportions of inorganic sorbent
materials or carriers based on silicate occur in the granules.
These sorbent materials or carriers have the disadvantages
demonstrated above.
[0022] In summary, it can be said that the state of the art
demonstrates no way of incorporating high proportions of liquid or
low melting point additives in solid formulations without having to
fall back on inorganic carrier systems. For this reason, the object
was to provide solid plant protection compositions with high
proportions of such additives.
[0023] Surprisingly, it has now been found that liquid or low
melting point polyalkoxylates, combined in suitable amounts with
relatively high molecular weight sulfonates, are able to provide
advantageous solid plant protection compositions, in particular
granules.
[0024] An object of the present invention is accordingly a solid
plant protection composition comprising a plant protection active
agent which comprises:
a) liquid or low melting point polyalkoxylate; and b) a carrier
based on relatively high molecular weight sulfonate, wherein [0025]
(i) the weight ratio of liquid or low melting point polyalkoxylate
to plant protection active agent is at least 1:2; [0026] (ii) the
proportion of liquid or low melting point polyalkoxylate, based on
the total weight of the relatively high molecular weight sulfonate,
is at least 30% by weight; and [0027] (iii) the weight ratio of
liquid or low melting point polyalkoxylate to relatively high
molecular weight sulfonate is at most 3:1.
[0028] The plant protection composition according to the invention
accordingly comprises, in addition to the active agent (component
(e)), basically two components: [0029] (a) a polyalkoxylate
component which, taken by itself, is liquid or has a low melting
point and consists of a polyalkoxylate or a mixture of several
polyalkoxylates; and [0030] (b) a carrier component which, taken by
itself, is solid and which comprises one or more relatively high
molecular weight sulfonates.
[0031] In this context, the proportion of liquid or low melting
point polyalkoxylate, based on the amount of active agent, is at
least 0.5, preferably at least 1 and in particular at least 2.
According to an additional aspect, the proportion of liquid or low
melting point polyalkoxylate is at least 15% by weight, based on
the total weight of the composition, and at least 30%, based on the
total weight of the relatively high molecular weight sulfonates. In
this context, the proportion of liquid or low melting point
polyalkoxylates can even be greater than the proportion of
relatively high molecular weight sulfonate, at most, however, up to
a weight ratio of 3:1. The carrier component (b) generally for the
most part comprises relatively high molecular weight sulfonate.
[0032] The term "liquid" describes the liquid physical state at
standard pressure and a temperature in the range from 20 to
30.degree. C. A low melting point polyalkoxylate generally has a
melting point of less than 40.degree. C., in particular of less
than 30.degree. C.
[0033] According to a particular embodiment, the polyalkoxylate to
be used is oily. In this context, the term "oily" describes a
viscous sticky-greasy physical consistency; chemically, the
substance can be looked at as lipophilic, hydrophilic or
amphiphilic. The polyalkoxylates are generally amphiphilic.
[0034] The polyalkoxylates according to the invention basically
comprise a hydrophobic or lipophilic portion and one or more
polymeric alkoxylate portions (polyalkoxylate or macrogol
portions), the polyalkoxylate portion or each individual
polyalkoxylate portion being coupled, for example via an amide,
ether or ester bond, to the hydrophobic or lipophilic portion. The
term "polymer" means in this context put together from at least
two, in particular at least three, very particularly from 3 to
1000, low molecular weight units. These units can either be all of
the same kind, so that a monotonic polymer is formed, or can
comprise at least two different types of alkylene oxide. In the
latter case, it is preferable each time to arrange several alkylene
oxide units of one type as a block, so that at least two different
alkylene oxide blocks ensue as structural elements of the polymer,
each of which consists of a monotonic sequence of identical
alkylene oxide units (block polymer or block copolymer). If such
block alkoxylates are used, it is preferable for the alkylene oxide
portion to be composed of 2 or 3 and in particular of 2 blocks. If
the polyalkoxylate portion comprises different blocks, those lying
closer to the hydrophobic or lipophilic portion are described as
"proximal", those lying further away are described as "distal" and
those positioned at the end are described as "terminal". Mention
may in particular be made here, as alkoxylate monomers according to
the invention, of ethylene oxide (EO), propylene oxide (PO),
butylene oxide (BO), pentylene oxide (PeO) and hexylene oxide
(HO).
[0035] Particular polyalkoxylates are found among alkoxylated fatty
alcohols, alkoxylated fatty acid esters, alkoxylated fatty amines,
alkoxylated glycerides, alkoxylated sorbitan esters, alkoxylated
alkylphenols and alkoxylated di- and tristyrylphenols, the
alkylphenols preferably being polyalkylated, in particular
dialkylated or trialkylated. Furthermore, the polyalkoxylates can
also be end-group-modified, i.e. the terminal OH group of the
alkoxylate portion is modified, for example etherified or
esterified. Suitable end-group-modified polyalkoxylates include in
particular alkylated, alkenylated or arylated polyalkoxylates,
preferably those with a methyl or tert-butyl group or a phenyl
group, or polyalkoxylate esters, e.g. mono- or diphosphate esters
or sulfate esters, and their salts, for example the alkali metal or
alkaline earth metal salts. Such an end-group modification can, for
example, be carried out with dialkyl sulfate, C.sub.1-10-alkyl
halide or phenyl halide.
[0036] At least some of the alcohol polyalkoxylates to be used are
known per se. For example, WO 01/77276 and U.S. Pat. No. 6,057,284
or EP 0 906 150 disclose suitable alcohol polyalkoxylates.
Reference is expressly made herewith to the description of these
alcohol polyalkoxylates in these documents, by which the alcohol
polyalkoxylates themselves and also their preparation disclosed
therein are part of the present disclosure.
[0037] In an additional particular embodiment, alcohol
polyalkoxylates are chosen from alcohol polyalkoxylates according
to the formula (I)
R.sup.7--O--(C.sub.mH.sub.2mO).sub.x--(C.sub.nH.sub.2nO).sub.y--(C.sub.p-
H.sub.2pO).sub.z--R.sup.6 (I)
in which R.sup.6 is an organic radical; R.sup.7 is an aliphatic
hydrocarbon radical with from 3 to 100 carbon atoms; m, n and p
are, independently of one another, a whole number from 2 to 6,
preferably 2, 3, 4 or 5; x, y and z are, independently of one
another, a number from 0 to 1000; and x+y+z corresponds to a value
from 2 to 1000.
[0038] The aliphatic hydrocarbon radical is generally hydrophobic
or lipophilic, by which the alcohol polyalkoxylates obtain their
oily properties. In particular, R.sup.1 is a branched or linear
hydrocarbon radical with from 3 to 30 and preferably from 5 to 24
carbon atoms which can be saturated (in particular
C.sub.3-30-alkyl) or unsaturated (in particular
C.sub.3-30-alkenyl).
[0039] The organic radical (R.sup.6) typically contributes less
than 10% and preferably less than 5% to the molecular weight of the
alcohol polyalkoxylate of the formula (I) and is preferably
hydrogen, alkyl, preferably C.sub.1-10-alkyl, particularly
preferably methyl or tert-butyl, alkenyl, preferably
C.sub.2-10-alkenyl, acyl, in particular acetyl, propionyl, butyryl
or benzoyl, or aryl, in particular phenyl, or is an inorganic acid
group, in particular phosphate, diphosphate or sulfate.
[0040] According to one aspect, it is preferable for the alcohol
polyalkoxylates to be used according to the invention to be
ethoxylated or to exhibit at least one ethylene oxide block.
According to an additional aspect, ethylene oxide blocks are
combined in particular with propylene oxide or pentylene oxide
blocks.
[0041] According to a particular embodiment, use is made of alcohol
polyalkoxylates of the formula (I) in which m=2 and x>0. In this
context, alcohol polyalkoxylates of EO type are concerned,
including above all alcohol ethoxylates (m=2; x>0; y, z=0) and
alcohol polyalkoxylates with a proximal EO block (m=2; x>0; y
and/or z>0).
[0042] Again, a particular embodiment of the alcohol
polyalkoxylates with a proximal EO block is represented by those
with a terminal block made from other monomers (n>2; y>0).
Mention may be made, among these, above all of EO-PO block
alkoxylates (n=3; y>0; z=0). Preference is given to EO-PO block
alkoxylates in which the ratio of EO to PO (x to y) is preferably
from 1:1 to 4:1 and in particular from 1.5:1 to 3:1. In this
context, the degree of ethoxylation (value of x) is generally from
1 to 20, preferably from 2 to 15 and in particular from 4 to 10 and
the degree of propoxylation (value of y) is generally from 1 to 20,
preferably from 1 to 8 and in particular from 2 to 5. The total
degree of alkoxylation, i.e. the sum of EO and PO units, is
generally from 2 to 40, preferably from 3 to 25 and in particular
from 6 to 15.
[0043] Mention may also be made, among the particularly preferred
alcohol polyalkoxylates with a proximal EO block, of EO-PeO block
alkoxylates (n=5; y>0; z=0). Preference is given in this context
to EO-PeO block alkoxylates in which the ratio of EO to PeO (x to
y) is preferably from 2:1 to 25:1 and in particular from 4:1 to
15:1. In this context, the degree of ethoxylation (value of x) is
generally from 1 to 50, preferably from 4 to 25 and in particular
from 6 to 15 and the degree of pentoxylation (value of y) is
generally from 0.5 to 20, preferably from 0.5 to 40 and in
particular from 0.5 to 2. The total degree of alkoxylation, i.e.
the sum of EO and PeO units, is generally from 1.5 to 70,
preferably from 4.5 to 29 and in particular from 6.5 to 17.
[0044] According to an additional particular embodiment, use is
made of alcohol polyalkoxylates of the formula (I) in which n=2,
the values of m, x and y are each time greater than zero and z=0.
In this context, alcohol polyalkoxylates of EO type are also
concerned in which the EO block is, though, distally bonded and an
additional polyalkoxylate block is inserted between it and the
alkyl part. These include above all PO-EO block alkoxylates and
PeO-EO block alkoxylates (n=2; x>0; y>0; m=5; z=0).
[0045] Again, a particular embodiment of such alcohol
polyalkoxylates with distal EO block is represented by PO-EO block
alkoxylates (n=2; x>0; y>0; m=3; z=0), in which the ratio of
PO to EO (x to y) is preferably from 1:10 to 3:1 and in particular
from 1.5:1 to 1:6. In this context, the degree of ethoxylation
(value of y) is generally from 1 to 20, preferably from 2 to 15 and
in particular from 4 to 10 and the degree of propoxylation (value
of x) is generally from 0.5 to 10, preferably from 0.5 to 6 and in
particular from 1 to 4. The total degree of alkoxylation, i.e. the
sum of EO and PO units, is generally from 1.5 to 30, preferably
from 2.5 to 21 and in particular from 5 to 14.
[0046] According to another particular embodiment, use is made of
alcohol polyalkoxylates of the formula (I) in which m=5 and x>0.
In this context, alcohol polyalkoxylates of PeO type are concerned.
Particular preference is given in this context to PeO-EO block
alkoxylates (n=2; y>0; z=0), in which the ratio of PeO to EO (x
to y) is from 1:50 to 1:3 and in particular from 1:25 to 1:5. In
this context, the degree of pentoxylation (value of x) is generally
from 0.5 to 20, preferably from 0.5 to 4 and in particular from 0.5
to 2 and the degree of ethoxylation (value of y) is generally from
3 to 50, preferably from 4 to 25 and in particular from 5 to 15.
The total degree of alkoxylation, i.e. the sum of EO and PeO units,
is generally from 3.5 to 70, preferably from 4.5 to 45 and in
particular from 5.5 to 17.
[0047] According to a particular embodiment, the alcohol
polyalkoxylates are not end-group-modified, i.e. R.sup.6 is
hydrogen.
[0048] According to a preferred embodiment of the invention, the
alcohol portion of the alcohol polyalkoxylates is based on alcohols
or mixtures of alcohols known per se with from 5 to 30, preferably
from 8 to 20 and in particular from 9 to 15 carbon atoms. Mention
may be made here in particular of fatty alcohols with from
approximately 8 to 20 carbon atoms. Many of these fatty alcohols
are, as is known, used for the preparation of nonionic and anionic
surfactants, for which the alcohols are subjected to an appropriate
functionalization, e.g. by alkoxylation or glycosidation.
[0049] The alcohol portion can be straight-chain, branched or
cyclic. If it is linear, mention may thus in particular be made of
alcohols with from 14 to 20, for example with from 16 to 18, carbon
atoms. If it is branched, the main chain of the alcohol portion
generally exhibits, according to a particular embodiment, from 1 to
4 branchings, it also being possible for alcohols with higher or
lower degrees of branching to be used in combination with
additional alcohol alkoxylates, provided that the average number of
the branchings of the mixture lies in the given range.
[0050] The alcohol portion can be saturated or unsaturated. If it
is unsaturated, it thus exhibits, according to a particular
embodiment, a double bond. Generally, the branchings of the alcohol
portion exhibit, independently of one another, each time from 1 to
10, preferably from 1 to 6 and in particular from 1 to 4 carbon
atoms. Particular branchings are methyl, ethyl, n-propyl or
isopropyl groups.
[0051] Suitable alcohols and in particular fatty alcohols can be
obtained both from native sources, e.g. by extraction, and
optionally, as necessary, by hydrolysis, transesterification and/or
hydrogenation of glycerides and fatty acids, and synthetically,
e.g. by synthesis from educts with a lower number of carbon atoms.
Thus, e.g., olefin fractions with a carbon number suitable for
further processing to give surfactants are obtained, starting from
ethers, according to the SHOP (Shell Higher Olefine Process)
process. The functionalization of the olefins to give the
corresponding alcohols is carried out in this context, e.g. by
hydroformylation and hydrogenation.
[0052] The alkoxylation results from the reaction with suitable
alkylene oxides. The prevailing degree of alkoxylation depends on
the dosages of alkylene oxide(s) chosen for the reaction and on the
reaction conditions. In this context, a statistical mean value is
generally concerned since the number of alkylene oxide units of the
alcohol polyalkoxylates resulting from the reaction varies.
[0053] The degree of alkoxylation, i.e. the mean chain length of
the polyether chains of the alcohol polyalkoxylates to be used
according to the invention, can be determined by the molar ratio of
alcohol to alkylene oxide. Preference is given to alcohol
polyalkoxylates with from approximately 2 to 100, preferably from
approximately 2 to 50, in particular from 3 to 30, above all from 4
to 20 and especially from 5 to 15 alkylene oxide units.
[0054] The reaction of the alcohols or alcohol mixtures with the
alkylene oxide(s) is carried out according to conventional
processes known to a person skilled in the art and using
conventional equipment therefor.
[0055] The alkoxylation reaction can be catalyzed by strong bases,
such as alkali metal hydroxides and alkaline earth metal
hydroxides, Bronsted acids or Lewis acids, such as AlCl.sub.3,
BF.sub.3, and the like. Catalysts such as hydrotalcite or DMC can
be used for narrowly distributed alcohol alkoxylates.
[0056] The alkoxylation is preferably carried out at temperatures
ranging from approximately 80 to 250.degree. C., preferably from
approximately 100 to 220.degree. C. The pressure is preferably
between ambient pressure and 600 bar. If desired, the alkylene
oxide can comprise an inert gas admixture, e.g. from approximately
5 to 60%.
[0057] According to a preferred embodiment, the alcohol
polyalkoxylates to be used according to the invention are based on
primary, .alpha.-branched alcohols of the formula (IV):
##STR00001##
in which R.sup.10 and R.sup.11 are, independently of one another,
hydrogen or C.sub.1-C.sub.26-alkyl.
[0058] Preferably, R.sup.10 and R.sup.11 are, independently of one
another, C.sub.1-C.sub.6-alkyl and in particular
C.sub.2-C.sub.4-alkyl.
[0059] According to a particular embodiment, use is made of alcohol
polyalkoxylates in which 2-propylheptanol is the alcohol portion.
These include in particular alcohol polyalkoxylates of the formula
(I) in which R.sup.7 is a 2-propylheptyl radical, i.e. each of
R.sup.10 and R.sup.11 in formula (IV) represent n-propyl.
[0060] Such alcohols are also described as Guerbet alcohols. These
can, for example, be obtained by dimerization of the corresponding
primary alcohols (e.g. R.sup.10,11--CH.sub.2CH.sub.2OH) at elevated
temperature, for example from 180 to 300.degree. C., in the
presence of an alkaline condensation catalyst, such as potassium
hydroxide. Within the framework of this preferred embodiment based
on Guebert alcohols, use is made in particular of alkoxylates of EO
type. Ethoxylates having a degree of ethoxylation of from 2 to 50,
preferably from 2 to 20 and in particular from approximately 3 to
10 are particularly preferred. Mention may expressly be made, among
these, of the appropriately ethoxylated 2-propylheptanols.
[0061] According to an additional particular embodiment, use is
made of alcohol polyalkoxylates in which the alcohol portion is a
C.sub.13-oxo alcohol.
[0062] It is particularly preferred for these C.sub.13-oxo alcohols
to be obtained by hydroformylation and subsequent hydrogenation of
unsaturated C.sub.12-hydrocarbons, in particular by hydrogenation
of hydroformylated trimeric butene or by hydrogenation of
hydroformylated dimeric hexene.
[0063] The term "C.sub.13-oxo alcohol" generally describes an
alcohol mixture, the main component of which is formed from at
least one C.sub.13-alcohol (isotridecanol). Such C.sub.13-alcohols
include in particular tetramethylnonanols, for example
2,4,6,8-tetramethyl-1-nonanol or 3,4,6,8-tetramethyl-1-nonanol, and
furthermore ethyldimethylnonanols, such as
5-ethyl-4,7-dimethyl-1-nonanol.
[0064] Suitable C.sub.13-alcohol mixtures can generally be obtained
by hydrogenation of hydroformylated trimeric butene. In particular,
it is possible [0065] 1) to bring butenes, for oligomerization,
into contact with a suitable catalyst, [0066] 2) to isolate a
C.sub.12-olefin fraction from the reaction mixture, [0067] 3) to
hydroformylate the C.sub.12-olefin fraction by reaction with carbon
monoxide and hydrogen in the presence of a suitable catalyst, and
[0068] 4) to hydrogenate.
[0069] The butene trimerization preceding the hydrogenation can be
carried out using homogeneous or heterogeneous catalysis.
[0070] A C.sub.12-olefin fraction is first isolated in one or more
separation stages from the reaction product of the oligomerization
reaction described, which fraction is then suitable for the
preparation, by hydroformylation and hydrogenation, of usable
C.sub.13-alcohol mixtures (process stage 2). The conventional
devices known to a person skilled in the art are suitable
separating devices.
[0071] The C.sub.12-olefin fraction thus isolated is
hydroformylated to give C.sub.13-aldehydes (process stage 3) and
subsequently hydrogenated to give C.sub.13-alcohols (process stage
4) for the preparation of an alcohol mixture according to the
invention. In this context, the alcohol mixtures can be prepared in
one stage or in two separate reaction stages.
[0072] A review of hydroformylation processes and suitable
catalysts appears in Beller et al., Journal of Molecular Catalysis
A, 104 (1995), pp. 17-85.
[0073] For the hydrogenation, the reaction mixtures obtained in the
hydroformylation are reacted with hydrogen in the presence of a
hydrogenation catalyst.
[0074] Additional suitable C.sub.13-alcohol mixtures can be
obtained by [0075] 1) subjecting a C.sub.4-olefin mixture to
metathesis, [0076] 2) separating olefins with 6 carbon atoms from
the metathesis mixture, [0077] 3) subjecting the separated olefins,
individually or in the mixture, to a dimerization to give olefin
mixtures with 12 carbon atoms, and [0078] 4) subjecting the olefin
mixture thus obtained, optionally after a fractionation, to the
derivatization to give a mixture of C.sub.13-oxo alcohols.
[0079] The C.sub.13-alcohol mixture according to the invention can
be obtained pure for use as component (a) from the mixture obtained
after the hydrogenation according to conventional purification
processes known to a person skilled in the art, in particular by
fractional distillation.
[0080] C.sub.13-alcohol mixtures according to the invention
generally exhibit a mean degree of branching of from 1 to 4,
preferably from 2.0 to 2.5 and in particular from 2.1 to 2.3 (based
on trimeric butene) or from 1.3 to 1.8 and in particular from 1.4
to 1.6 (based on dimeric hexene). The degree of branching is
defined as number of the methyl groups in a molecule of the alcohol
minus 1. The mean degree of branching is the statistical mean value
of the degrees of branching of the molecules of a sample. The mean
number of the methyl groups in the molecules of a sample can be
readily determined by .sup.1H NMR spectroscopy. For this, the
signal area corresponding to the methyl protons in the .sup.1H NMR
spectrum of a sample is divided by 3 and compared with the signal
area, divided by 2, of the methylene protons in the CH.sub.2--OH
group.
[0081] Within the framework of this particular embodiment based on
C.sub.13-oxo alcohols, preference is given in particular to those
alcohol alkoxylates which are either ethoxylated or are block
alkoxylates of EO/PO type.
[0082] The degree of ethoxylation of the ethoxylated C.sub.13-oxo
alcohols to be used according to the invention is generally from 1
to 50, preferably from 3 to 20 and in particular from 3 to 10,
especially from 4 to 10 and particularly from 5 to 10.
[0083] The degrees of alkoxylation of the EO/PO block alkoxylates
to be used according to the invention depend on the arrangement of
the blocks. If the PO blocks are terminally arranged, the ratio of
EO units to PO units is thus generally at least 1, preferably from
1:1 to 4:1 and in particular from 1.5:1 to 3:1. In this context,
the degree of ethoxylation is generally from 1 to 20, preferably
from 2 to 15 and in particular from 4 to 10 and the degree of
propoxylation is generally from 1 to 20, preferably from 1 to 8 and
in particular from 2 to 5. The total degree of alkoxylation, i.e.
the sum of EO and PO units, is generally from 2 to 40, preferably
from 3 to 25 and in particular from 6 to 15. On the other hand, if
the EO blocks are terminally arranged, the ratio of PO blocks to EO
blocks is less critical and is generally from 1:10 to 3:1,
preferably from 1:1.5 to 1:6. In this context, the degree of
ethoxylation is generally from 1 to 20, preferably from 2 to 15 and
in particular from 4 to 10 and the degree of propoxylation is
generally from 0.5 to 10, preferably from 0.5 to 6 and in
particular from 1 to 4. The total degree of alkoxylation is
generally from 1.5 to 30, preferably from 2.5 to 21 and in
particular from 5 to 14.
[0084] According to an additional particular embodiment, use is
made of alcohol polyalkoxylates in which the alcohol portion is a
C.sub.10-oxo alcohol. The term "C.sub.10-oxo alcohol" represents,
analogously to the term "C.sub.13-oxo alcohol" already explained,
C.sub.10-alcohol mixtures having a main component formed from at
least one branched C.sub.10-alcohol (isodecanol).
[0085] It is particularly preferable for suitable C.sub.10-alcohol
mixtures to be obtained by hydrogenation of hydroformylated
trimeric propene.
[0086] In particular, it is possible [0087] 1) to bring propenes
into contact with a suitable catalyst for the purpose of
oligomerization, [0088] 2) to isolate a C.sub.9-olefin fraction
from the reaction mixture, [0089] 3) to hydroformylate the
C.sub.9-olefin fraction by reaction with carbon monoxide and
hydrogen in the presence of a suitable catalyst, and [0090] 4) to
hydrogenate.
[0091] Particular embodiments of this procedure ensue by analogy to
the embodiments described above for the hydrogenation of
hydroformylated trimeric butene.
[0092] Within the framework of this particular embodiment based on
C.sub.10-oxo alcohols, preference is given in particular to those
alcohol alkoxylates which are either ethoxylated or are block
alkoxylates of EO/PeO type.
[0093] The degree of ethoxylation of the ethoxylated C.sub.10-oxo
alcohols to be used according to the invention is generally from 2
to 50, preferably from 2 to 20 and in particular from 2 to 10,
especially from 3 to 10 and particularly from 3 to 10.
[0094] The degrees of alkoxylation of the EO/PeO block alkoxylates
to be used according to the invention depend on the arrangement of
the blocks. If the PeO blocks are terminally arranged, the ratio of
EO units to PeO units is thus generally at least 1, preferably from
2:1 to 25:1 and in particular from 4:1 to 15:1. In this context,
the degree of ethoxylation is generally from 1 to 50, preferably
from 4 to 25 and in particular from 6 to 15 and the degree of
pentoxylation is generally from 0.5 to 20, preferably from 0.5 to 4
and in particular from 0.5 to 2. The total degree of alkoxylation,
i.e. the sum of EO and PeO units, is generally from 1.5 to 70,
preferably from 4.5 to 29 and in particular from 6.5 to 17. On the
other hand, if the EO blocks are terminally arranged, the ratio of
PeO blocks to EO blocks is less critical and is generally from 1:50
to 1:3, preferably from 1:25 to 1:5. In this context, the degree of
ethoxylation is generally from 3 to 50, preferably from 4 to 25 and
in particular from 5 to 15 and the degree of pentoxylation is
generally from 0.5 to 20, preferably from 0.5 to 4 and in
particular from 0.5 to 2. The total degree of alkoxylation is
generally from 3.5 to 70, preferably from 4.5 to 45 and in
particular from 5.5 to 17.
[0095] It follows, from the above embodiments, that in particular
the C.sub.13-oxo alcohols or C.sub.10-oxo alcohols to be used
according to the invention are based on olefins which are already
branched. In other words, branchings are not only to be traced back
to the hydroformylation reaction, as would be the case in the
hydroformylation of straight chain olefins. Consequently, the
degree of branching of the alkoxylates to be used according to the
invention is generally greater than 1.
[0096] The alkoxylates to be used according to the invention
generally exhibit a relatively low contact angle. Particular
preference is given to alkoxylates having a contact angle of less
than 120.degree. and preferably of less than 100.degree. when this
is determined in a way known per se on a paraffin surface for an
aqueous solution comprising 2% by weight of alkoxylate.
[0097] According to one aspect, the surface-active properties of
the polyalkoxylates depend on the type and distribution of the
polyalkoxylate grouping. The surface tension of the polyalkoxylates
to be used according to the invention, which can be determined
according to the pendant drop method, preferably ranges from 25 to
70 mN/m and in particular from 28 to 50 mN/m for a solution
comprising 0.1% by weight of polyalkoxylate and ranges from 25 to
70 mN/m and in particular from 28 to 45 mN/m for a solution
comprising 0.5% by weight of polyalkoxylate. Polyalkoxylates
preferably to be used according to the invention accordingly
qualify as amphiphilic substances.
[0098] Typical commercial products of the formula (I) are familiar
to a person skilled in the art. They are, e.g., offered for sale by
BASF under the general brand name of the "Lutensoles", Lutensoles
of the series A, AO, AT, ON, AP and FA being differentiated
according to the base alcohol. Furthermore, included numbers give
the degree of ethoxylation. Thus, e.g., "Lutensol AO 8" is a
C.sub.13-15-oxo alcohol with eight EO units. "Lutensol ED"
represents a series of alkoxylated amines.
[0099] Additional examples of polyalkoxylates according to the
invention are products from Akzo, e.g. the "Ethylan" series based
on linear or branched alcohols. Thus, e.g., "Ethylan SN 120" is a
C.sub.10-12-alcohol with ten EO units and "Ethylan 4 S" is a
C.sub.12-14-alcohol with four EO units.
[0100] Additional examples of polyalkoxylates according to the
invention are furthermore the "NP" products from Akzo (formerly
Witco) based on nonylphenols. Nonylphenol alkoxylates or analogous
monoalkylphenol alkoxylates and their derivatives are not preferred
for use in Europe since European approving authorities are
assessing them very critically with regard to their potential
endocrinal effects. With regard to this, di- or
polyalkyl-substituted aryl or polyaryl alkoxylates, which are not
criticized, are preferred for Europe.
[0101] Additional examples of polyalkoxylates according to the
invention are castor oil ethoxylates (castor oil-EO.sub.x), e.g.
products of the "Emulphon CO" or "Emulphon EL" product series from
Akzo, such as, for example, "Emulphon CO 150" with 15 EO units, or
products of the "Ethomee" series based on coconut oil amines or
tallow oil amines, e.g. "Ethomee C/25", a coconut oil amine with 25
EO units.
[0102] Alkoxylates according to the invention also comprise "narrow
range" products. The expression "narrow range" refers in this
context to a fairly narrow distribution in the number of the EO
units. These include, e.g., products of the "Berol" series from
Akzo.
[0103] Furthermore, sorbitan ester ethoxylates, e.g. "Armotan AL
69-66 POE(30) sorbitan monotallate", thus an unsaturated fatty acid
esterified with sorbitol and subsequently ethoxylated, are
according to the invention.
[0104] Mixtures of different polyalkoxylates can also be used as
component (a).
[0105] According to a particular embodiment of the invention, the
composition comprises at least 20% by weight, preferably at least
25% by weight and in particular at least 30% by weight of
alkoxylate.
[0106] According to an additional particular embodiment of the
invention, the composition comprises at most 70% by weight,
preferably at most 60% by weight and in particular at most 45% by
weight of alkoxylate.
[0107] Use may generally be made, as carrier component (b), of
solid, relatively high molecular weight, for example polymeric or
macromolecular, organic sulfonates. The term "sulfonate" here
represents a salt which is composed of sulfonate anions and
suitable cations.
[0108] In this context, it is particularly preferable for the
relatively high molecular weight sulfonate to be soluble in water.
The sulfonates according to the invention, in contrast to typical
carriers, which are generally based on water-insoluble inorganic
solids, can accordingly be introduced in dissolved form, preferably
as aqueous concentrates, in the preparation of the solid plant
protection compositions, through which they function particularly
effectively as carriers of the component (a).
[0109] Suitable relatively high molecular weight sulfonates
generally exhibit a weight-average molecular weight (determined by
means of gel permeation chromatography calibrated with
polystyrenesulfonates) of at least ca. 1 kDa, preferably of at
least ca. 2.5 kDa and in particular of at least ca. 5 kDa, for
example a weight-average molecular weight of ca. 6-7 kDa (e.g.
"Tamol NN" series), or of ca. 20 kDa (e.g. "Tamol NH" series).
According to an additional aspect, suitable relatively high
molecular weight sulfonates exhibit, for example, a number-average
molecular weight (determined by means of gel permeation
chromatography calibrated with polystyrenesulfonates) of ca. 1 kDa
(e.g. "Tamol NN" series) or of ca. 2 kDa (e.g. "Tamol NH" series),
so that the polydispersity index of suitable relatively high
molecular weight sulfonates generally ranges from ca. 2 to 20 and
preferably ranges from 5 to 15, for example is ca. 6 (e.g. "Tamol
NN" series) or is ca. 20 (e.g. "Tamol NH" series). Additional
properties of suitable relatively high molecular weight sulfonates
are, for example, a bulk density of ca. 450-ca. 550 g/l for solids
or a density of ca. 1.17-ca. 1.23 g/ml and a viscosity of ca.
20-ca. 80 mPas for liquids, and also a neutral to alkaline behavior
(pH value in aqueous solution ca. 7-10).
[0110] According to a preferred embodiment of the invention,
lignosulfonates are used.
[0111] Lignosulfonates are produced from lignin which, in turn,
arises in plants, especially in woody plants, by polymerization
from three types of phenylpropanol monomers: [0112] A)
3-(4-hydroxyphenyl)-2-propen-1-ol (p-cumaryl alcohol), [0113] B)
3-(3-methoxy-4-hydroxyphenyl)-2-propen-1-ol (coniferyl alcohol),
[0114] C) 3-(3,5-dimethoxy-4-hydroxyphenyl)-2-propen-1-ol (sinapyl
alcohol).
[0115] The first step in the synthesis of the macromolecular lignin
structure consists in enzymatically dehydrogenating these monomers,
producing phenoxyl radicals. Random coupling reactions between
these radicals lead to a three-dimensional amorphous polymer which,
in contrast to most other biopolymers, exhibits no regularly
arranged or repeated units. For this reason, no defined lignin
structure can be mentioned, although various models for an
"average" structure have been proposed. Since the monomers of the
lignin comprise nine carbon atoms, the analytical data is often
expressed in terms of C.sub.9-formulae, e.g.
C.sub.9H.sub.8.3O.sub.2.7(OCH.sub.3).sub.0.97 for lignin from Picea
abies and C.sub.9H.sub.8.7O.sub.2.9(OCH.sub.3).sub.1.58 for lignin
from Eucalyptus regnans.
[0116] The lack of uniformity of the lignin between plants of
different taxa, just as between the different tissues, cells and
cell wall layers of any one species, is familiar to a person
skilled in the art. Lignins from coniferous trees, broad-leaved
trees and grasses differ with regard to their content of guaiacyl
(3-methoxy-4-hydroxyphenyl), syringyl
(3,5-dimethoxy-4-hydroxyphenyl) and 4-hydroxyphenyl units. Lignins
from coniferous trees are composed mainly of coniferyl alcohol,
while lignins from broad-leaved trees are composed of guaiacyl and
syringyl units in different ratios, the composition of the lignin
being considerably more variable in broad-leaved trees than in
coniferous trees. The methoxyl content of typical lignins from
broad-leaved trees varies between 1.20 and 1.52 methoxyl groups per
phenylpropane unit. Lignins from herbaceous plants generally have a
low content of syringylpropanes with a ratio of methoxyl to C.sub.9
units of less than 1.
[0117] The composition of the lignin also depends on the age, e.g.
in poplars, the ratio of syringyl to guaiacyl in mature xylem is
higher than in young xylem or phloem, and on the morphological
position of the lignin in the cell wall. For example, in birch, the
lignin in the secondary cell wall of fiber cells is composed mostly
of syringyl units, while that in middle lamellae and cell corners
of the fibers comprises mainly guaiacyl units. Lignin from wood
under tension, in broad-leaved trees in the upper parts of the
twigs and branches, comprises more syringylpropane units than the
lignin from normal wood; wood under pressure, in coniferous trees
in the lower parts of the twigs and branches, is, on the other
hand, richer in 4-hydroxyphenyl units.
[0118] More than two-thirds of the phenylpropane units in lignin
are linked via ether bonds and the remainder via carbon-carbon
bonds.
[0119] The chemical behavior of the lignin is mainly determined by
the presence of phenolic, benzylic and carbonylic hydroxyl groups,
the frequency of which can vary depending on the abovementioned
factors and the method of isolation.
[0120] Lignosulfonates are formed as byproducts in the manufacture
of pulp under the action of sulfurous acid, which causes
sulfonation and a certain amount of demethylation of the lignins.
Like the lignins, they are varied in structure and composition.
They are soluble in water over the entire pH range; on the other
hand, they are insoluble in ethanol, acetone and other common
organic solvents. The following C.sub.9 formula is typical for
coniferous lignosulfonates:
C.sub.9H.sub.8.5O.sub.2.5(OCH.sub.3).sub.0.85(SO.sub.3H).sub.0.4;
e.sub.280=3.0.times.10.sup.3 L (C.sub.9 unit of weight).sup.-1
cm.sup.-1; .lamda..sub.max=280 nm; phenol hydroxyl content 0.5
meq./g.
[0121] Lignosulfonates are only slightly surface-active. They have
only a slight tendency to reduce the boundary tension between
liquids and are not suitable for reducing the surface tension of
water or for micelle formation. They can function as dispersants by
adsorption/desorption and charge formation of substrates. However,
their surface activity can be increased by introduction of
long-chain alkyl amines into the lignin structure.
[0122] Methods for the isolation and purification of
lignosulfonates are familiar to a person skilled in the art. In the
Howard process, calcium lignosulfonates are precipitated by
addition of an excess of lime to spent sulfite waste liquor.
Lignosulfonates can also be isolated by formation of insoluble
quaternary ammonium salts with long-chain amines. On the industrial
scale, ultrafiltration and ion-exchange chromatography can be used
for the purification of lignosulfonates.
[0123] Lignosulfonate series which can be used according to the
invention are commercially available under a number of trade names,
such as, e.g., Ameri-Bond, Dynasperse, Kelig, Lignosol, Marasperse,
Norlig (Daishowa Chemicals), Lignosite (Georgia Pacific), Reax
(Mead Westvaco), Wafolin, Wafex, Wargotan, Wanin, Wargonin
(Holmens), Vanillex (Nippon Paper), Vanisperse, Vanicell,
Ultrazine, Ufoxane (Borregaard), Serla-Bondex, Serla-Con,
Serla-Pon, Serla-Sol (Serlachius), Collex, Zewa (Wadhof-Holmes) or
Raylig (ITT Rayonier).
[0124] According to an additional preferred embodiment of the
invention, synthetic polymeric sulfonates are used as component
(b).
[0125] In this context, it is again particularly preferable for the
relatively high molecular weight sulfonate to be a condensation
product based on a sulfonated aromatic compound, an aldehyde and/or
ketone and, if appropriate, on a compound chosen from nonsulfonated
aromatic compounds, urea and urea derivatives.
[0126] In this context, it is particularly preferable for the
sulfonated aromatic compound to be chosen from naphthalenesulfonic
acids, indansulfonic acids, tetralinsulfonic acids, phenolsulfonic
acids, di- and polyhydroxybenzenesulfonic acids, sulfonated ditolyl
ethers, sulfomethylated 4,4'-dihydroxydiphenyl sulfones, sulfonated
diphenylmethane, sulfonated biphenyl, sulfonated hydroxybiphenyl,
sulfonated terpenyl and benzenesulfonic acids.
[0127] It is also particularly preferable for the aldehyde and/or
the ketone to be chosen from aliphatic C.sub.1-C.sub.5-aldehydes or
C.sub.3-C.sub.5-ketones. In this context, it is again particularly
preferable for the aliphatic C.sub.1-C.sub.5-aldehyde to be
formaldehyde.
[0128] Furthermore, it is particularly preferable for the
nonsulfonated aromatic compound to be chosen from phenol, cresol
and dihydroxydiphenylmethane. Furthermore, it is particularly
preferable for the urea derivative to be chosen from
dimethylolurea, melamine and guanidine.
[0129] In a particular embodiment, the condensation product
comprises repetitive units according to formula (IIa):
##STR00002##
and/or formula (IIb):
##STR00003##
and/or formula (IIc):
##STR00004##
in which R.sup.8 is hydrogen, one or more hydroxyl groups or one or
more C.sub.1-8-alkyl radicals; q1 corresponds to a value from 100
to 10.sup.10; and A is methylene, 1,1-ethylene or a group of the
formulae
##STR00005##
[0130] In the above formulae, the positions of the bonds are not
specified.
[0131] Preferably, A is methylene. It is likewise preferable for
R.sup.8 to be hydrogen or up to 3 C.sub.1-8-alkyl radicals, for
example 1 or 2 C.sub.1-4 alkyl radicals.
[0132] Such condensation products and the processes and devices for
their preparation are familiar per se to a person skilled in the
art.
[0133] In an additional particular embodiment, the condensation
product comprises repetitive units according to formula (III):
##STR00006##
in which R.sup.9 is hydrogen, one or more hydroxyl groups or one or
more C.sub.1-8-alkyl radicals; q2 corresponds to a value from 100
to 10.sup.10; A is methylene, 1,1-ethylene or a group of the
formulae
##STR00007##
[0134] In the above formulae, the positions of the bonds are not
specified.
[0135] It is preferable for R.sup.9 to be a hydroxyl group.
[0136] In an additional particular embodiment, the sulfonate is
chosen from the group consisting of condensation products of
phenolsulfonic acid, formaldehyde and urea. Such condensation
products preferably comprise repetitive units according to formula
(IIIa):
##STR00008##
in which q2 corresponds to a value from 100 to 10.sup.10.
[0137] Such condensation products and the processes and devices for
their preparation are also familiar per se to a person skilled in
the art.
[0138] An additional embodiment of relatively high molecular weight
sulfonates provides copolymers CP synthesized from ethylenically
unsaturated monomers M, the monomers M constituting the copolymer
CP comprising [0139] .alpha.) at least one monoethylenically
unsaturated monomer M1 exhibiting at least one sulfonic acid group,
and [0140] .beta.) at least one neutral monoethylenically
unsaturated monomer M2.
[0141] The copolymers CP are generally "random copolymers", i.e.
the monomers M1 and M2 are randomly distributed along the polymer
chain. In principle, alternating copolymers CP and block copolymers
CP are also suitable.
[0142] The monomers M constituting the copolymer CP comprise
according to the invention at least one monoethylenically
unsaturated monomer M1 exhibiting at least one sulfonic acid group.
The proportion of the monomers M1 to the monomers M in this context
generally amounts to from 1 to 90% by weight, frequently from 1 to
80% by weight, in particular from 2 to 70% by weight and especially
from 5 to 60% by weight, based on the total amount of monomers
M.
[0143] In this context, all monoethylenically unsaturated monomers
exhibiting at least one sulfonic acid group are suitable in
principle as monomers M1. The monomers M1 can exist both in their
acid form and in the salt form. The parts by weight given are based
in this context on the acid form.
[0144] Examples of monomers M1 are styrenesulfonic acid,
vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid and
the monomers defined by the following general formula (V) and the
salts of the abovementioned monomers.
##STR00009##
[0145] In formula (V): [0146] n represents 0, 1, 2 or 3, in
particular 1 or 2; [0147] X represents O or NR.sup.15; [0148]
R.sup.12 represents hydrogen or methyl; [0149] R.sup.13 and
R.sup.14 represent, independently of one another, hydrogen or
C.sub.1-C.sub.4-alkyl, in particular hydrogen or methyl, and [0150]
R.sup.15 represents hydrogen or C.sub.1-C.sub.4-alkyl, in
particular hydrogen.
[0151] Examples of monomers M1 of the general formula (V) are
2-acrylamido-2-methylpropanesulfonic acid,
2-methacrylamido-2-methylpropanesulfonic acid,
2-acrylamidoethanesulfonic acid, 2-methacrylamidoethanesulfonic
acid, 2-acryloyloxyethanesulfonic acid,
2-methacryloyloxyethanesulfonic acid, 3-acryloyloxypropanesulfonic
acid and 2-methacryloyloxypropanesulfonic acid.
[0152] In addition to the monomers M1, the monomers M constituting
the copolymer CP comprise at least one neutral monoethylenically
unsaturated monomer M2. "Neutral" means that the monomers M2
possess no functional group which reacts as an acid or base under
aqueous conditions or is present in ionic form. The total amount of
the monomers M2 generally comes to from 10 to 99% by weight,
frequently from 20 to 99% by weight, in particular from 30 to 98%
by weight and especially from 40 to 95% by weight, based on the
total weight of the monomers M.
[0153] Examples of monomers M2 are those with limited solubility in
water, e.g. a solubility in water of less than 50 g/l and in
particular of less than 30 g/l (at 20.degree. C. and 1013 mbar),
and those with an elevated solubility in water, e.g. a solubility
in water .gtoreq.50 g/l, in particular .gtoreq.80 g/l (at
20.degree. C. and 1013 mbar). Monomers with limited solubility in
water are also described subsequently as monomers M2a. Monomers
with elevated solubility in water are also described subsequently
as monomers M2b.
[0154] Examples of monomers M2a are vinylaromatic monomers, such as
styrene and styrene derivatives, such as .alpha.-methylstyrene,
vinyltoluene, ortho-, meta- and para-methyl-styrene,
ethylvinylbenzene, vinylnaphthalene, vinylxylene and the
corresponding halogenated vinylaromatic monomers, .alpha.-olefins
with from 2 to 12 carbon atoms, such as ethene, propene, 1-butene,
1-pentene, 1-hexene, isobutene, diisobutene and the like, dienes,
such as butadiene and isoprene, vinyl esters of aliphatic
C.sub.1-C.sub.18-carboxylic acids, such as vinyl acetate, vinyl
propionate, vinyl laurate and vinyl stearate, vinyl halides, such
as vinyl chloride, vinyl fluoride, vinylidene chloride or
vinylidene fluoride, mono- and di-C.sub.1-C.sub.24-alkyl esters of
monoethylenically unsaturated mono- and dicarboxylic acids, e.g. of
acrylic acid, of methacrylic acid, of fumaric acid, of maleic acid
or of itaconic acid, mono- and di-C.sub.5-C.sub.12-cycloalkyl
esters of the abovementioned monoethylenically unsaturated mono-
and dicarboxylic acids, mono- and diesters of the abovementioned
monoethylenically unsaturated mono- and dicarboxylic acids with
phenyl-C.sub.1-C.sub.4-alkanols or
phenoxy-C.sub.1-C.sub.4-alkanols, and furthermore monoethylenically
unsaturated ethers, in particular C.sub.1-C.sub.20-alkyl vinyl
ethers, such as ethyl vinyl ether, methyl vinyl ether, n-butyl
vinyl ether, octadecyl vinyl ether, triethylene glycol vinyl methyl
ether, vinyl isobutyl ether, vinyl 2-ethylhexyl ether, vinyl propyl
ether, vinyl isopropyl ether, vinyl dodecyl ether or vinyl
tert-butyl ether.
[0155] The monomers M2a are preferably chosen from vinylaromatic
monomers, esters of acrylic acid with C.sub.2-C.sub.10-alkanols,
such as ethyl acrylate, n-butyl acrylate, 2-butyl acrylate,
isobutyl acrylate, tert-butyl acrylate or 2-ethylhexyl acrylate,
esters of acrylic acid with C.sub.4-C.sub.10-cycloalkanols, such as
cyclohexyl acrylate, esters of acrylic acid with
phenyl-C.sub.1-C.sub.4-alkanols, such as benzyl acrylate,
2-phenylethyl acrylate and 1-phenyl-ethyl acrylate, esters of
acrylic acid with phenoxy-C.sub.1-C.sub.4-alkanols, such as
2-phenoxyethyl acrylate, esters of methacrylic acid with
C.sub.1-C.sub.10-alkanols, in particular with
C.sub.1-C.sub.6-alkanols, such as methyl methacrylate, ethyl
methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl
methacrylate, tert-butyl methacrylate or 2-ethylhexyl methacrylate,
esters of methacrylic acid with C.sub.4-C.sub.10-cycloalkanols,
such as cyclohexyl methacrylate, esters of methacrylic acid with
phenyl-C.sub.1-C.sub.4-alkanols, such as benzyl methacrylate,
2-phenylethyl methacrylate and 1-phenylethyl methacrylate, and
esters of methacrylic acid with phenoxy-C.sub.1-C.sub.4-alkanols,
such as 2-phenoxyethyl methacrylate. In a particularly preferred
embodiment, the monomers M2a comprise up to at least 80%, based on
the total amount of the monomers M2a, of and in particular
exclusively esters of acrylic acid and/or of methacrylic acid with
C.sub.1-C.sub.6-alkanols.
[0156] Neutral monoethylenically unsaturated monomers with
increased solubility in water or even miscibility in water are
known to a person skilled in the art, e.g. from Ullmann's
Encyclopedia of Industrial Chemistry, "Polyacrylates", 5th ed. on
CD-ROM, Wiley-VCH, Weinheim, 1997. Typical monomers M2b are
hydroxy-C.sub.2-C.sub.4-alkyl esters of monoethylenically
unsaturated monocarboxylic acids, in particular of acrylic acid and
of methacrylic acid, such as 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 3-hydroxy-propyl acrylate, 2-hydroxybutyl
acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate,
2-hydroxybutyl methacrylate or 4-hydroxybutyl methacrylate,
furthermore amides of monoethylenically unsaturated monocarboxylic
acids, such as acrylamide or methacrylamide, furthermore
acrylonitrile and methacrylonitrile, N-vinyllactams, such as
N-vinylpyrrolidone or N-vinylcaprolactam, N-vinylamides of
aliphatic C.sub.1-C.sub.4-mono-carboxylic acids, such as
N-vinylformamide or N-vinylacetamide, monoethylenically unsaturated
monomers carrying urea groups, such as N-vinyl- and N-allylurea,
and also derivatives of imidazolidin-2-one, e.g. N-vinyl- and
N-allylimidazolidin-2-one, N-vinyloxyethylimidazolidin-2-one,
N-allyloxyethylimidazolidin-2-one,
N-(2-acrylamido-ethyl)imidazolidin-2-one,
N-(2-acryloyloxyethyl)imidazolidin-2-one,
N-(2-methacrylamidoethyl)imidazolidin-2-one,
N-(2-methacryloyloxyethyl)imidazolidin-2-one (=ureidomethacrylate),
N-[2-(acryloyloxyacetamido)ethyl]imidazolidin-2-one,
N-[2-(2-acryloyloxyacetamido)ethyl]imidazolidin-2-one or
N-[2-(2-methacryloyloxyacetamido)ethyl]imidazolidin-2-one; and the
like. The monomers M2b are preferably chosen from
hydroxy-C.sub.1-C.sub.4-alkyl esters of acrylic acid and of
methacrylic acid, acrylamide, methacrylamide, acrylonitrile or
N-vinyllactam, the hydroxy-C.sub.2-C.sub.4-alkyl esters of acrylic
acid and of methacrylic acid being particularly preferred. In
particular, the monomers M2b comprise up to at least 80% by weight,
based on the total amount of the monomers M2b, of at least one
hydroxy-C.sub.2-C.sub.4-alkyl ester of acrylic acid and/or of
methacrylic acid.
[0157] Preferably, the monomers M2 comprise at least one of the
abovementioned monomers M2a exhibiting, at 20.degree. C. in water,
a solubility of less than 50 g/l and in particular of less than 30
g/l. The proportion of the monomers M2a in the monomers M
constituting the copolymer CP typically ranges from 10 to 99% by
weight, frequently ranges from 20 to 99% by weight, in particular
ranges from 30 to 98% by weight and especially ranges from 40 to
95% by weight, based on the total weight of the monomers M.
[0158] In a first preferred embodiment of the invention, the
monomer M2a is sole or virtually sole monomer M2 and amounts to at
least 95% by weight and in particular at least 99% by weight of the
monomers M2.
[0159] In a second preferred embodiment of the invention, the
monomers M2 comprise, in addition to the monomer M2a, at least one
monomer M2b exhibiting, at 20.degree. C. in water, a solubility of
at least 50 g/l and in particular of at least 80 g/l.
Correspondingly, the monomers M constituting the copolymer CP
comprise, in addition to the monomer M1, both at least one of the
abovementioned monomers M2a, in particular at least one of the
monomers M2a mentioned as preferred, and at least one of the
abovementioned monomers M2b, in particular at least one of the
monomers M2b mentioned as preferred.
[0160] The total amount of the monomers M1+M2b will frequently not
exceed 90% by weight, in particular 80% by weight and especially
70% by weight, based on the total amount of the monomers M, and
ranges in particular from 10 to 90% by weight, in particular from
20 to 80% by weight and especially from 30 to 70% by weight, based
on the total amount of the monomers M. Correspondingly, the
monomers M2a frequently come to at least 10% by weight, in
particular at least 20% by weight and especially at least 30% by
weight, e.g. from 10 to 90% by weight, in particular from 20 to 80%
by weight and especially from 30 to 70% by weight, based on the
total amount of the monomers M.
[0161] In this second particularly preferred embodiment, the
monomers M1 preferably come to from 1 to 80% by weight, in
particular from 2 to 70% by weight and particularly preferably from
5 to 60% by weight, the monomers M2a preferably come to from 10 to
90% by weight, in particular from 20 to 80% by weight and
particularly preferably from 30 to 70% by weight, and the monomers
M2b preferably come to from 5 to 89% by weight, in particular from
10 to 78% by weight and particularly preferably from 20 to 65% by
weight, based on the total amount of the monomers M. Particular
preference is given among these to copolymers CP, the constituent
monomers M of which comprise, as monomers M1, at least one monomer
of the formula (V), as monomers M2a, at least one monomer chosen
from esters of acrylic acid with C.sub.2-C.sub.10-alkanols and
esters of methacrylic acid with C.sub.1-C.sub.10-alkanols and, as
monomers M2b, at least one monomer chosen from
hydroxy-C.sub.2-C.sub.4-alkyl esters of acrylic acid and of
methacrylic acid.
[0162] In addition, the monomers M constituting the copolymer can
comprise yet further monomers M3 differing from the monomers M1 and
M2. The proportion of the monomers M3 in the total amount of the
monomers M preferably comes to not more than 40% by weight, in
particular not more than 20% by weight. In a preferred embodiment,
the monomers comprise no or not more than 3% by weight, especially
not more than 1% by weight, of monomers M3 differing from the
monomers M1 and M2.
[0163] The monomers M3 include monoethylenically unsaturated
monomers with at least one carboxylic group, in particular
monoethylenically unsaturated mono- and dicarboxylic acids with
from 3 to 6 carbon atoms (monomers M3a), such as acrylic acid,
methacrylic acid, vinylacetic acid, crotonic acid, fumaric acid,
maleic acid, itaconic acid and the like, and the anhydrides of the
abovementioned monoethylenically unsaturated dicarboxylic acids,
the proportion of the monomers M3a generally not exceeding 20% by
weight and in particular 10% by weight, based on the total amount
of monomers M.
[0164] The monomers M3 furthermore include polyethylenically
unsaturated monomers (M3b). The proportion of such monomers M3 will
generally be not more than 2% by weight and in particular not more
than 0.5% by weight, based on the total amount of monomers M.
Examples of these are vinyl and allyl esters of monoethylenically
unsaturated carboxylic acids, such as allyl acrylate and allyl
methacrylate, di- and polyacrylates of di- or polyols, such as
ethylene glycol diacrylate, ethylene glycol dimethacrylate,
butanediol diacrylate, butanediol dimethacrylate, hexanediol
diacrylate, hexanediol dimethacrylate, triethylene glycol
diacrylate, triethylene glycol dimethacrylate,
tris(hydroxymethyl)ethane triacrylate and trimethacrylate, or
pentaerythritol triacrylate and trimethacrylate, and furthermore
the allyl and methallyl esters of polyfunctional carboxylic acids,
such as diallyl maleate, diallyl fumarate or diallyl phthalate.
Typical monomers M3b are also compounds such as divinylbenzene,
divinylurea, diallylurea, triallyl cyanurate, N,N'-divinyl- and
N,N'-diallylimidazolidin-2-one, and also methylenebisacrylamide and
methylenebismethacrylamide.
[0165] Preference is furthermore given according to the invention
to copolymers CP exhibiting a number-average molecular weight
M.sub.n ranging from 1000 to 500 000 daltons, in particular from
2000 to 50 000 daltons and especially from 5000 to 20 000 daltons.
The weight-average molecular weight frequently ranges from 2000 to
1 000 000 daltons, in particular from 4000 to 100 000 daltons and
especially from 10 000 to 50 000 daltons. The ratio M.sub.w/M.sub.n
frequently ranges from 1.1:1 to 10:1, in particular from 1.2:1 to
5:1.
[0166] The molar masses M.sub.w and M.sub.n and the lack of
uniformity of the polymers are determined by size exclusion
chromatography (=gel permeation chromatography or just GPC).
Commercial poly(methyl methacrylate) (PMMA) standard units can be
used as calibration material.
[0167] Generally, the copolymer according to the invention will
exhibit a glass transition temperature T.sub.g ranging from
-80.degree. C. to 160.degree. C. and frequently ranging from
-40.degree. C. to +100.degree. C. The term "glass transition
temperature T.sub.g" is understood here to mean the "midpoint
temperature" determined according to ASTM D 3418-82 by differential
scanning calorimetry (DSC) (cf. Ullmann's Encyclopedia of
Industrial Chemistry, 5th Edition, Volume A 21, VCH Weinheim, 1992,
p. 169, and also Zosel, Farbe und Lack, 82 (1976), pp. 125-134, see
also DIN 53765).
[0168] In this context, it proves to be helpful to estimate the
glass transition temperature T.sub.g of the copolymer CP with the
help of the Fox equation (T. G. Fox, Bull. Am. Phys. Soc. (Ser.
II), 1, 123 [1956], and Ullmann's Encyclopedia of Industrial
Chemistry, Weinheim (1980), pp. 17-18) from the glass transition
temperatures of the respective homopolymers of the monomers M
constituting the polymer. The latter are known, e.g., from
Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol.
A 21 (1992), p. 169, or from J. Brandrup and E. H. Immergut,
Polymer Handbook, 3rd ed., J. Wiley, New York, 1989.
[0169] The copolymers CP according to the invention are in some
cases known from PCT/EP04/011797 or can be prepared according to
conventional methods by radical polymerization of the monomers M.
The polymerization can be carried out by free radical
polymerization or by controlled radical polymerization processes.
The polymerization using one or more initiators and can be carried
out as solution polymerization, as emulsion polymerization, as
suspension polymerization, as precipitation polymerization or as
bulk polymerization. The polymerization can be carried out
batchwise, semicontinuously or continuously.
[0170] The reaction times generally range between 1 and 12 hours.
The temperature range in which the reactions can be carried out
generally extends from 20 to 200.degree. C., preferably from 40 to
120.degree. C. The polymerization pressure is of secondary
importance and can be carried out in the range from standard
pressure or slight negative pressure, e.g. >800 mbar, or under
positive pressure, e.g. up to 10 bar, it being possible for higher
or lower pressures likewise to be used.
[0171] Conventional radical-forming substances are used as
initiators for the radical polymerization. Preference is given to
initiators from the group of the azo compounds, of the peroxide
compounds or of the hydroperoxide compounds. Mention may be made,
by way of examples, of acetyl peroxide, benzoyl peroxide, lauryl
peroxide, tert-butylperoxy isobutyrate, caproyl peroxide, cumene
hydroperoxide, 2,2'-azobisisobutyronitrile,
2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],
1,1'-azobis(1-cyclohexanecarbonitrile),
2,2'-azobis(2,4-dimethylvaleronitrile) or
2,2'-azobis(N,N'-dimethyleneisobutyroamidine).
Azobisisobutyronitrile (AIBN) is particularly preferred. The
initiator is normally used in an amount of from 0.02 to 5% by
weight and in particular from 0.05 to 3% by weight, based on the
amount of the monomers M. The optimum amount of initiator naturally
depends on the initiator system used and can be determined by a
person skilled in the art in routine experiments. The initiator can
be partially or completely provided within the reaction vessel.
Preferably, the bulk of the initiator, in particular at least 80%,
e.g. from 80 to 100%, of the initiator, is added to the
polymerization reactor in the course of the polymerization.
[0172] The molecular weight of the copolymer CP can self-evidently
be adjusted by addition of a small amount of regulators, e.g. from
0.01 to 5% by weight, based on the polymerizing monomers M.
Suitable regulators are in particular organic thio compounds, e.g.
mercaptoalcohols, such as mercaptoethanol, mercaptocarboxylic
acids, such as thioglycolic acid or mercaptopropionic acid, or
alkyl mercaptans, such as dodecyl mercaptan, and furthermore allyl
alcohols and aldehydes.
[0173] The copolymers CP are prepared in particular by radical
solution polymerization in a solvent. Examples of solvents are
water, alcohols, such as, e.g., methanol, ethanol, n-propanol and
isopropanol, dipolar aprotic solvents, e.g. N-alkyllactams, such as
N-methylpyrrolidone (NMP) or N-ethylpyrrolidone, furthermore
dimethyl sulfoxide (DMSO) or N,N-dialkylamides of aliphatic
carboxylic acids, such as N,N-dimethyl-formamide (DMF) or
N,N-dimethylacetamide, or furthermore aromatic, aliphatic and
cycloaliphatic hydrocarbons which may be halogenated, such as
hexane, chlorobenzene, toluene or benzene. Preferred solvents are
isopropanol, methanol, toluene, DMF, NMP, DMSO and hexane. DMF is
particularly preferred.
[0174] As salts, the sulfonates comprise cations in a
stoichiometric amount. Examples of suitable cations are alkali
metal cations, such as Na.sup.+ or K.sup.+, alkaline earth metal
ions, such as Ca.sup.2+ and Mg.sup.2+, furthermore ammonium ions,
such as NH.sub.4.sup.+, tetraalkylammonium cations, such as
tetramethylammonium, tetraethylammonium and tetrabutylammonium, or
furthermore protonated primary, secondary and tertiary amines, in
particular those carrying 1, 2 or 3 radicals chosen from
C.sub.1-C.sub.20-alkyl groups and hydroxyethyl groups, e.g. the
protonated forms of mono-, di- and tributylamine, propylamine,
diisopropylamine, hexylamine, dodecylamine, oleylamine,
stearylamine, ethoxylated oleylamine, ethoxylated stearylamine,
ethanolamine, diethanolamine, triethanolamine or
N,N-dimethylethanolamine.
[0175] In a preferred embodiment of the invention, the sulfonate is
an ammonium, alkali metal, alkaline earth metal or transition metal
sulfonate.
[0176] In this context, it is particularly preferable each time for
the alkali metal to be sodium or potassium, for the alkaline earth
metal to be calcium or magnesium and for the transition metal to be
copper.
[0177] Mixtures of different sulfonates can also be used as
component (b).
[0178] Suitable sulfonates are familiar to a person skilled in the
art and are available, e.g. under the names "Tamol" and "Setamol",
from BASF.
[0179] Examples of polymers comprising sulfonic acid which are
suitable in principle as component (b) are also mentioned in EP 707
445.
[0180] In this context, it is particularly preferable for the plant
protection composition to comprise at least 15% by weight,
preferably at least 25% by weight and in particular at least 30% by
weight of relatively high molecular weight sulfonate.
[0181] In this context, it is also particularly preferable for the
plant protection composition to comprise at most 80% by weight,
preferably at most 70% by weight and in particular at most 55% by
weight of relatively high molecular weight sulfonate.
[0182] The plant protection compositions according to the invention
comprise relatively high amounts of polyalkoxylate. It is
preferable, based on the amount of relatively high molecular weight
sulfonate, for the ratio by weight of liquid or low melting point
polyalkoxylate to relatively high molecular weight sulfonate to be
at least 3:10, preferably at least 1:3 and particularly preferably
1:2. The ratio of liquid or low melting point polyalkoxylate to
relatively high molecular weight sulfonate should, though, not be
more than 3:1, preferably not be more than 2:1.
[0183] In one embodiment of the invention, a portion of the
sulfonate in the carrier component (b) can be replaced by inorganic
solid. In this embodiment, the component (b), in addition to the
relatively high molecular weight sulfonate (b1), also comprises
inorganic solid (b2).
[0184] Possible inorganic solids in the carrier component (b) are
in particular those which are conventionally used in solid plant
protection compositions for taking up liquid or low melting point,
in particular oily, auxiliaries, such as the polyalkoxylates
according to the invention (carriers). In this context, inorganic
solids which make possible adsorption of aforementioned auxiliaries
(sorbent materials) are mainly concerned.
[0185] Suitable inorganic solids are generally sparingly soluble or
insoluble in water, i.e. at least 100, generally at least 1000 and
in particular at least 10 000 parts of water are necessary to
dissolve one part of inorganic solid at 20.degree. C. However, the
sparingly soluble or even water-insoluble inorganic solids can be
swellable in water.
[0186] The inorganic solids include in particular substances based
on aluminum oxide, in particular aluminum oxide and bauxite, and
substances based on silicon dioxide, in particular silicates and
silicate minerals, above all diatomaceous earths (kieselguhr,
diatomite), silicas, pyrophyllite, talc, mica and clays, such as
kaolinite, bentonite, montmorillonite and attapulgite. Some
inorganic salts, for example alkaline earth metal carbonates, in
particular calcium carbonates (limestone, chalk) and magnesium
carbonates, and also calcium magnesium carbonates, and alkaline
earth metal sulfates, in particular calcium sulfates (e.g. gypsum),
are also suitable in principle. Mention may be made, among the
silicates, for example, of the products of the Sipernat series
(Degussa), in particular Sipernat 22S or 50S, which can typically
be used for these purposes.
[0187] The proportion of the inorganic solids suitable as component
(b2) listed above can according to the invention, though, be chosen
to be comparatively low since the relatively high molecular weight
sulfonates function essentially as carriers of the polyalkoxylates.
In addition, further advantages become apparent on avoiding high
proportions of inorganic solids.
[0188] To this effect, the weight-related proportion of the
relatively high molecular weight sulfonate in the component (b) is
generally greater than the weight-related proportion of inorganic
solid; according to the invention, the weight ratio of relatively
high molecular weight sulfonate to inorganic solid is preferably at
least 2, preferably at least 5 and in particular at least 10.
[0189] In particular, it is preferable for the composition
altogether to comprise less than 10% by weight, in particular less
than 5% by weight, of aluminium oxide based substances and
particularly preferable for the composition altogether to be
essentially free of aluminum oxide based substances.
[0190] It is also preferable for the composition altogether to
comprise less than 5% by weight, in particular less than 2% by
weight, of diatomaceous earths and particularly preferable for the
composition altogether to be essentially free of diatomaceous
earths. It is also preferable for the composition altogether to
comprise less than 5% by weight, in particular less than 1% by
weight, of kaolinite and particularly preferable for the
composition altogether to be essentially free of kaolinite. It is
also preferable for the composition altogether to comprise less
than 5% by weight, in particular less than 1% by weight, of
bentonites and particularly preferable for the composition
altogether to be essentially free of bentonites.
[0191] It is also preferable for the composition altogether to
comprise less than 7.5% by weight, in particular less than 1.5% by
weight, of clays and particularly preferable for the composition to
be essentially free of clays.
[0192] It is also preferable for the composition altogether to
comprise less than 15% by weight, in particular less than 2% by
weight, of substances based on silicon dioxide and particularly
preferable for the composition to be essentially free of substances
based on silicon dioxide.
[0193] According to a particular embodiment, the composition
comprises altogether less than 15% by weight, in particular less
than 10% by weight and particularly preferably less than 5% by
weight of the following inorganic solids: substances based on
aluminum oxide, in particular aluminum oxide and bauxite, and
substances based on silicon dioxide, in particular silicates and
silicate minerals, above all diatomaceous earths (kieselguhr,
diatomite), silicas, pyrophillite, talc, mica and clays, such as
kaolinite, bentonite, montmorillonite and attapulgite.
[0194] It is preferable for the composition altogether to comprise
less than 1% by weight of sorbent materials and particularly
preferable for the composition altogether to be essentially free of
sorbent materials.
[0195] Furthermore, it is preferable for the composition altogether
to comprise less than 5% by weight, in particular less than 1% by
weight, of calcium carbonate and particularly preferable for the
composition altogether to be essentially free of calcium carbonate.
Furthermore, it is also preferable for the composition altogether
to comprise less than 5% by weight, in particular less than 1% by
weight, of magnesium carbonate and particularly preferable for the
composition altogether to be essentially free of magnesium
carbonate.
[0196] According to a particular embodiment, the composition
comprises altogether less than 10% by weight, in particular less
than 5% by weight and particularly preferably less than 1% by
weight of the following inorganic solids: alkali metal and alkaline
earth metal carbonates, in particular calcium carbonates
(limestone, chalk) and magnesium carbonates, as well as calcium
magnesium carbonates, and alkali metal and alkaline earth metal
sulfates, in particular calcium sulfates (e.g. gypsum).
[0197] In this context, it is very particularly preferable for the
composition to comprise altogether at most 15% by weight,
preferably altogether at most 10% by weight and especially at most
5% by weight, e.g. at most 1% by weight, of inorganic solid and
especially for the carrier component (b) to be essentially free of
inorganic solid.
[0198] According to a particular embodiment, the present invention
relates to a plant protection composition which, in addition to the
components a) and b), can comprise additional auxiliary as
component c).
[0199] The optional component (c) can serve a multitude of
purposes. Generally, component (c) accordingly is composed of a
combination of several materials with different functions and
properties. The choice of suitable auxiliaries is made
conventionally by a person skilled in the art according to the
requirements.
[0200] The following are suitable in particular as component (c):
[0201] c1) surface-active auxiliaries; [0202] c2) suspension
agents, antifoaming agents, retention agents, pH buffers, drift
retardants and other auxiliaries for improving the handleability
and/or physical properties of the composition; and [0203] c3)
chelating agents.
[0204] The term "surface-active auxiliaries" (c1) describes here
surface-active agents such as surfactants, dispersants, emulsifiers
or wetters.
[0205] Anionic, cationic, amphoteric and nonionic surfactants can
be used in principle.
[0206] The anionic surfactants include, for example: [0207]
carboxylates, in particular alkali metal, alkaline earth metal and
ammonium salts of fatty acids; [0208] acyl glutamates; [0209]
sarcosinates, e.g. sodium lauryl sarcosinate; [0210] taurates;
[0211] methylcelluloses; [0212] alkyl phosphates, e.g.
monophosphoric acid alkyl esters and hypophosphoric acid alkyl
esters; [0213] sulfates; [0214] monomeric sulfonates, in particular
alkyl- and alkylarylsulfonates, above all alkali metal, alkaline
earth metal and ammonium salts of arylsulfonic acids and
alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids,
such as, for example, phenolsulfonic acids, naphthalene- and
dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates,
alkylnaphthalenesulfonates, alkyl methyl ester sulfonates, or mono-
or dialkylsuccinic acid ester sulfonates; [0215] protein
hydrolysates and spent lignosulfite waste liquors.
[0216] The cationic surfactants include, for example: [0217]
quaternary ammonium salts, in particular alkyltrimethylammonium and
dialkyl-dimethylammonium halides and alkyl sulfates, and [0218]
pyridine and imidazoline derivatives, in particular alkylpyridinium
halides.
[0219] The nonionic surfactants include in particular: [0220]
glycerol esters, such as, for example, glycerol monostearate;
[0221] sugar surfactants, in particular sorbitol esters, such as,
for example, sorbitan fatty acid esters (sorbitan monooleate,
sorbitan tristearate), and esters of mono- or polyhydric alcohols,
such as alkyl(poly)glycosides and N-alkylgluconamides; [0222] alkyl
methyl sulfoxides; [0223] alkyldimethylphosphine oxides, such as,
for example, tetradecyldimethyl-phosphine oxide; [0224] di-, tri-
and multiblock polymers of the (AB).sub.x, ABA and BAB type, e.g.
poly-styrene-block-polyethylene oxide, and AB comb polymers, e.g.
polymethacrylate-comb-polyethylene oxide, and in particular
ethylene oxide/propylene oxide block copolymers or their end-capped
derivatives.
[0225] The amphoteric surfactants include, for example: [0226]
sulfobetaines; [0227] carboxybetaines, and [0228]
alkyldimethylamine oxides, e.g. tetradecyldimethylamine oxide.
[0229] Additional surfactants which may be mentioned here by way of
example, without being able to be unambiguously assigned to one of
the groups mentioned, comprise: [0230] perfluorinated surfactants,
[0231] silicone surfactants, [0232] phospholipids, such as, e.g.,
lecithin or chemically modified lecithins, [0233] amino acid
surfactants, e.g. N-lauroylglutamate, and [0234] surface-active
homo- and copolymers, e.g. polyvinylpyrrolidone, polyacrylic acids
in the form of their salts, polyvinyl alcohol, polypropylene oxide,
poly-ethylene oxide, maleic anhydride/isobutene copolymers and
vinylpyrrolidone/vinyl acetate copolymers.
[0235] Furthermore, the following are possible, inter alia, as
wetters: dioctyl sulfosuccinate (e.g., "Pelex OTP"),
dialkylsulfonimide ("Leophen RBD"), diisobutylnaphthalene-sulfonate
("Nekal BX"), various alkylalkynols ("Surfynol", Bisterfeld),
alkylarylphenol ether phosphate esters ("Phospholan PNP") and
polyethylene glycol ("Pluriol"), and also combinations of the
materials mentioned.
[0236] The proportion of the surface-active auxiliary component
(c1) in the total weight of the composition, if present, is
generally up to 25% by weight, preferably up to 20% by weight, in
particular up to 15% by weight and especially up to 10% by weight,
based on the total weight of the composition.
[0237] Such surface-active auxiliary components are in some cases
contained in active agent suspensions and preconcentrates which are
used in combination with the ingredients according to the
invention. Alternatively, they can be added separately in a
suitable stage of the preparation of the composition.
[0238] The antifoaming agents include in particular those of the
silicone type, for example the Silicon SL sold by Wacker and the
like.
[0239] The suspension agents, retention agents, pH buffers and
drift retardants comprise a multitude of possible substances. They
are familiar to a person skilled in the art.
[0240] Additional auxiliaries from (c2) are, e.g., antidusting
agents, supporting substances, polymers for improving the structure
of granules, coating agents or polymeric flow improvers for
granules. Such auxiliaries are described in the state of the art
and are familiar to a person skilled in the art. Hydrophilic
pyrogenic silicas, such as the Aerosil brands (Degussa), can also
function as auxiliaries and/or antiblocking agents.
[0241] The proportion of the surface-active auxiliary component
(c2) in the total weight of the composition, if present, is
generally up to 15% by weight, preferably up to 10% by weight and
in particular up to 5% by weight, based on the total weight of the
composition.
[0242] Preferred chelating agents are compounds which complex heavy
metals and in particular transition metals, e.g. EDTA and its
derivatives.
[0243] If present, the proportion of the component (c3) in the
total weight of the composition is generally from 0.001 to 0.5% by
weight, preferably from 0.005 to 0.2% by weight and in particular
from 0.01 to 0.1% by weight.
[0244] It is generally preferable for the composition altogether to
comprise at most 60% by weight, preferably at most 45% by weight
and in particular at most 30% by weight of additional auxiliary
(c).
[0245] Typically, the ratio by weight of (a) and (b) to (c) is at
least 3, preferably at least 5.
[0246] According to a particular embodiment, the present invention
relates to a solid plant protection composition which, in addition
to the components a), b) and, if appropriate, c), can comprise
water-soluble inorganic salt as component d).
[0247] An inorganic salt is then water-soluble if less than 20
parts of water, in particular less than 10 parts of water, are
necessary to dissolve one part of inorganic salt at 20.degree. C.
Possible water-soluble inorganic salts of the component (d) are in
particular those which can be used agriculturally, for example
minerals which can be made use of by plants and trace elements.
[0248] Suitable water-soluble inorganic salts occur in particular
among alkali metal and ammonium salts, particularly preferably
sodium, potassium and ammonium sulfates, chlorides, carbonates,
nitrates and phosphates, particularly preferably again ammonium
sulfate and ammonium hydrogensulfate, and their mixtures. According
to a particular embodiment, the component (d) is composed
essentially of ammonium sulfate.
[0249] If present, the proportion of the component (d) in the total
weight of the composition can be up to 65% by weight. Preferably,
its proportion in the total weight of the composition is up to 50%
by weight, preferably up to 28.5% by weight and particularly
preferably up to 25% by weight, e.g. 0% by weight-17.5% by
weight.
[0250] The component (d) is particularly suitable as base solid for
fluidized bed granules. The water-soluble inorganic salt can
accordingly serve as nucleus for the forming process during the
fluidized bed drying since, in the fluidized bed drying, no de novo
formation of defined particles from the fluid phase is possible
without introduction of a solid core for attachment to or a
fluidized bed process without addition of solid nuclei does not
result in usable particle size distributions.
[0251] Solid plant protection compositions with relatively low
proportions of component (d) certainly represent a preferred
embodiment. To this effect, the proportion of the component (d) in
the overall composition is from 0 to 10% by weight, preferably from
0 to 5% by weight and in particular from 0 to 2% by weight, e.g. 0%
by weight-1% by weight. In this embodiment, the water-soluble
inorganic salts nevertheless present are not generally of
particular importance in the sense of the formulation. Typically,
they are frequently included as a result of the preparation, i.e.
they are incorporated together with other components according to
the invention.
[0252] Consequently, it is preferable for the composition
altogether to comprise less than 5% by weight, in particular less
than 2% by weight, of sodium chloride and particularly preferable
for the composition altogether to be essentially free of sodium
chloride. It is consequently also preferable for the composition
altogether to comprise less than 5% by weight, in particular less
than 2% by weight, of potassium chloride and particularly
preferable for the composition altogether to be essentially free of
potassium chloride. It is consequently also preferable for the
composition altogether to comprise less than 5% by weight, in
particular less than 2% by weight, of sodium carbonate and
particularly preferable for the composition altogether to be
essentially free of sodium carbonate. It is consequently also
preferable for the composition altogether to comprise less than 5%
by weight, in particular less than 2% by weight, of potassium
hydrogenphosphate and particularly preferable for the composition
altogether to be essentially free of potassium
hydrogenphosphate.
[0253] According to a particular embodiment, the composition
altogether comprises less than 10% by weight, in particular less
than 5% by weight and particularly preferably less than 1% by
weight of the following water-soluble inorganic solids: alkali
metal and alkaline earth metal halides, in particular sodium
chloride and potassium chloride, alkali metal sulfates, e.g. sodium
sulfate, alkali metal carbonates, e.g. sodium carbonate, and alkali
metal and alkaline earth metal phosphates, in particular potassium
hydrogenphosphate.
[0254] In this context, any substance may be described as plant
protection active agent (pesticide) of the component (e) which has
the purpose or effect of preventing infection of a plant by any
pest or of repelling, deterring or destroying the pest or of
reducing in another way the damage caused by it. As stated above,
plant pests can belong to different groups of organisms; the higher
animals, in particular insects and acarids, include numerous
important pests, as do nematodes and snails; vertebrates, such as
mammals and birds, are today of secondary importance in
industrialized countries. Numerous groups of microbes, including
fungi, bacteria, inclusive of mycoplasmas, viruses and viroids,
comprise pests, and even weeds, which compete with useful plants
for limited habitat and other resources, can be classed as pests in
the broad sense. Pesticides comprise in particular avicides,
acaricides, desiccants, bactericides, chemosterilants, defoliants,
antifeedants, fungicides, herbicides, herbicide safeners, insect
attractants, insecticides, insect repellents, molluscicides,
nematicides, mating disrupters, plant activators, plant growth
regulators, rodenticides, mammal repellents, synergists, bird
repellents and virucides.
[0255] Pesticides comprise, classified according to chemical
classes, in particular acylalanine fungicides, acylamino acid
fungicides, aliphatic amide organothiophosphate insecticides,
aliphatic organothiophosphate insecticides, aliphatic nitrogen
fungicides, amide fungicides, amide herbicides, anilide fungicides,
anilide herbicides, inorganic fungicides, inorganic herbicides,
inorganic rodenticides, antiauxins, antibiotic acaricides,
antibiotic fungicides, antibiotic herbicides, antibiotic
insecticides, antibiotic nematicides, aromatic acid fungicides,
aromatic acid herbicides, arsenical herbicides, arsenical
insecticides, arylalanine herbicides, aryloxyphenoxypropionic acid
herbicides, auxins, avermectin acaricides, avermectin insecticides,
benzamide fungicides, benzanilide fungicides, benzimidazole
fungicides, benzimidazole precursor fungicides,
benzimidazolylcarbamate fungicides, benzoic acid herbicides,
benzofuranyl alkylsulfonate herbicides, benzofuranyl
methylcarbamate insecticides, benzothiazole fungicides,
benzothiopyran organothiophosphate insectides, benzotriazine
organothio-phosphate insecticides, benzoylcyclohexanedione
herbicides, bipyridylium herbicides, bridged diphenyl acaricides,
bridged diphenyl fungicides, carbamate acaricides, carbamate
fungicides, carbamate herbicides, carbamate insecticides, carbamate
nematicides, carbanilate fungicides, carbanilate herbicides,
quinolinecarboxylate herbicides, quinoline fungicides, quinone
fungicides, quinoxaline acaricides, quinoxaline organothiophosphate
insecticides, quinoxaline fungicides, chitin synthesis inhibitors,
chloracetanilide herbicides, chloronicotinyl insecticides,
chloropyridine herbicides, chlorotriazine herbicides, conazole
fungicides, coumarin rodenticides, cyclodithiocarbamate fungicides,
cyclohexane oxime herbicides, cyclopropylisoxazole herbicides,
cytokinins, diacylhydrazine insecticides, dicarboximide fungicides,
dicarboximide herbicides, dichlorophenyl dicarboximide fungicides,
dimethylcarbamate insecticides, dinitroaniline herbicides,
dinitrophenol acaricides, dinitrophenol fungicides, dinitrophenol
herbicides, dinitrophenol insecticides, diphenyl ether herbicides,
dithiocarbamate fungicides, dithiocarbamate herbicides, defoliants,
ethylene releasers, fluorine insecticides, furamide fungicides,
furanilide fungicides, gibberellins, halogenated aliphatic
herbicides, urea fungicides, urea herbicides, urea insecticides,
urea rodenticides, moulting hormones, moulting hormone mimics,
moulting inhibitors, heterocyclic organothiophosphate insecticides,
imidazole fungicides, imidazolinone herbicides, indandione
rodenticides, insect growth regulators, isoindole
organothiophosphate insecticides, isoxazole organothiophosphate
insecticides, juvenile hormones, juvenile hormone mimics, copper
fungicides, macrocyclic lactone acaricides, macrocyclic lactone
insecticides, methoxytriazine herbicides, methylthiotriazine
herbicides, milbemycin acaricides, milbemycin insecticides, mite
growth regulators, morphactins, morpholine fungicides, nereistoxin
analogues, nicotinoid insecticides, nitrile herbicides,
nitroguanidine insecticides, nitromethylene insecticides,
nitrophenyl ether herbicides, organochlorine acaricides,
organochlorine insecticides, organochlorine rodenticides,
organophosphate acaricides, organophosphate insecticides,
organophosphate nematicides, organophosphorus acaricides,
organophosphorus fungicides, organophosphorus herbicides,
organophosphorus insecticides, organophosphorus nematicides,
organophosphorus rodenticides, organothiophosphate acaricides,
organothiophosphate insecticides, organothiophosphate nematicides,
organotin acaricides, organotin fungicides, oxadiazine
insecticides, oxathiine fungicides, oxazole fungicides, oxime
carbamate acaricides, oxime carbamate nematicides, oxime carbamate
insecticides, oxime organothiophosphate insecticides, botanical
insecticides, botanical rodenticides, phenoxybutyric acid
herbicides, phenoxyacetic acid herbicides, phenoxy herbicides,
phenoxypropionic acid herbicides, phenylenediamine herbicides,
phenyl ethylphosphonothioate insecticides, phenylurea herbicides,
phenyl methylcarbamate insecticides, phenyl organothiophosphate
insecticides, phenyl phenylphosphonothioate insecticides, phenyl
pyrazolyl ketone herbicides, phenylsulfamide acaricides,
phenylsulfamide fungicides, phosphonate acaricides, phosphonate
insecticides, phosphonothioate insecticides, phosphoramidate
insecticides, phosphoramidothioate acaricides, phosphoramidothioate
insecticides, phosphorodiamide acaricides, phosphorodiamide
insecticides, phthalate herbicides, phthalimide acaricides,
phthalimide fungicides, phthalimide insecticides, picolate
herbicides, polymeric dithiocarbamate fungicides, polysulfide
fungicides, precocenes, pyrazole acaricides, pyrazole fungicides,
pyrazole insecticides, pyrazolopyrimidine organothiophosphate
insecticides, pyrazolyloxyacetophenone herbicides, pyrazolylphenyl
herbicides, pyrethroid acaricides, pyrethroid ester acaricides,
pyrethroid ester insecticides, pyrethroid ether acaricides,
pyrethroid ether insecticides, pyrethroid insecticides, pyridazine
herbicides, pyridazinone herbicides, pyridine fungicides, pyridine
herbicides, pyridine organothiophosphate insecticides,
pyridylmethylamine insecticides, pyrimidinamine acaracides,
pyrimidinamine insecticides, pyrimidinamine rodenticides,
pyrimidinediamine herbicides, pyrimidine organothiophosphate
insecticides, pyrimidine fungicides, pyrimidinyloxybenzoic acid
herbicides, pyrimidinylsulfonylurea herbicides,
pyrimidinylthiobenzoic acid herbicides, pyrrole acaricides, pyrrole
fungicides, pyrrole insecticides, quaternary ammonium herbicides,
strobilurin fungicides, sulfite ester acaricides, sulfonamide
fungicides, sulfonamide herbicides, sulfonanilide fungicides,
sulfonanilide herbicides, sulfonylurea herbicides, tetrazine
acaracides, tetronate acaricides, tetronate insecticides,
thiadiazole organothiophosphate insecticides, thiadiazolylurea
herbicides, thiazole fungicides, thiocarbamate acaricides,
thiocarbamate fungicides, thiocarbamate herbicides, thiocarbonate
herbicides, thiourea acaricides, thiourea herbicides, thiourea
rodenticides, thiophene fungicides, triazine fungicides, triazine
herbicides, triazinone herbicides, triazinylsulfonylurea
herbicides, triazole fungicides, triazole herbicides, triazolone
herbicides, triazolopyrimidine herbicides, triazole
organothiophosphate insecticides, uracil herbicides, valinamide
fungicides, growth inhibitors, growth stimulators, growth
retardants and xylylalanine fungicides.
[0256] The pesticide for use according to the invention is chosen
in particular from fungicides (e1), herbicides (e2) and
insecticides (e3).
[0257] Fungicides comprise, for example, aliphatic nitrogen
fungicides, such as butylamine, cymoxanil, dodicin, dodine,
guazatine or iminoctadine; amide fungicides, such as carpropamid,
chloraniformethan, cyflufenamid, diclocymet, ethaboxam, fenoxanil,
flumetover, furametpyr, mandipropamid, penthiopyrad, prochloraz,
quinazamid, silthiofam or triforine; in particular acylamino acid
fungicides, such as benalaxyl, benalaxyl-M, furalaxyl, metalaxyl,
metalaxyl-M or pefurazoate; anilide fungicides, such as benalaxyl,
benalaxyl-M, boscalid, carboxin, fenhexamid, metalaxyl,
metalaxyl-M, metsulfovax, ofurace, oxadixyl, oxycarboxin,
pyracarbolid, thifluzamide or tiadinil; in particular benzanilide
fungicides, such as benodanil, flutolanil, mebenil, mepronil,
salicylanilide or tecloftalam; furanilide fungicides, such as
fenfuram, furalaxyl, furcarbanil or methfuroxam; and sulfonanilide
fungicides, such as flusulfamide; benzamide fungicides, such as
benzohydroxamic acid, fluopicolide, tioxymid, trichlamide,
zarilamid or zoxamide; furamide fungicides, such as cyclafuramid or
furmecyclox; phenylsulfamide fungicides, such as dichlofluanid or
tolylfluanid; sulfonamide fungicides, such as cyazofamid; and
valinamide fungicides, such as benthiavalicarb or iprovalicarb;
antibiotic fungicides, such as aureofungin, blasticidin-S,
cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxins,
polyoxorim, streptomycin or validamycin; in particular strobilurin
fungicides, such as azoxystrobin, dimoxystrobin, fluoxastrobin,
kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin,
pyraclostrobin or trifloxystrobin; aromatic fungicides, such as
biphenyl, chlorodinitronaphthalene, chloroneb, chlorothalonil,
cresol, dicloran, quintozene or tecnazene; benzimidazole
fungicides, such as benomyl, carbendazim, chlorfenazole,
cypendazole, debacarb, fuberidazole, mecarbinzid, rabenzazole or
thiabendazole; benzimidazole precursor fungicides, such as
furophanate, thiophanate or thiophanate-methyl; benzothiazole
fungicides, such as bentaluron, chlobenthiazone or TCMTB; bridged
diphenyl fungicides, such as bithionol, dichlorophen or
diphenylamine; carbamate fungicides, such as benthiavalicarb,
furophanate, iprovalicarb, propamocarb, thiophanate or
thiophanate-methyl; in particular benzimidazolyl-carbamate
fungicides, such as benomyl, carbendazim, cypendazole, debacarb or
mecarbinzid; and carbanilate fungicides, such as diethofencarb;
conazole fungicides; in particular imidazoles, such as climbazole,
clotrimazole, imazalil, oxpoconazole, prochloraz or triflumizole;
and triazoles, such as azaconazole, bromuconazole, cyproconazole,
diclobutrazol, difenoconazole, diniconazole, diniconazole-M,
epoxiconazole, etaconazole, fenbuconazole, fluquinconazole,
flusilazole, flutriafol, furconazole, furconazol-cis, hexaconazole,
imibenconazole, ipconazole, metconazole, myclobutanil, penconazole,
propiconazole, prothioconazole, quinconazole, simeconazole,
tebuconazole, tetraconazole, triadimefon, triadimenol,
triticonazole, uniconazole or uniconazole-P; copper fungicides,
such as Bordeaux mixture, Burgundy mixture, Cheshunt mixture,
copper acetate, copper carbonate, copper hydroxide, copper
naphthenate, copper oleate, copper oxychloride, copper sulfate,
copper zinc chromate, copper oxide, mancopper, cufraneb, cuprobam
or oxine-copper; dicarboximide fungicides, such as famoxadone or
fluoroimide; in particular dichlorophenyl carboximide fungicides,
such as chlozolinate, dichlozoline, iprodione, isovaledione,
myclozolin, procymidone or vinclozolin; and phthalimide fungicides,
such as captafol, captan, ditalimfos, folpet or thiochlorfenphim;
dinitrophenol fungicides, such as binapacryl, dinobuton, dinocap,
dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon
or DNOC; dithiocarbamate fungicides, such as azithiram, carbamorph,
cufraneb, cuprobam, disulfuram, ferbam, metam, nabam, tecoram,
thiram or ziram; in particular cyclodithiocarbamate fungicides,
such as dazomet, etem or milneb; and polymeric dithiocarbamate
fungicides, such as mancopper, mancozeb, maneb, metiram,
polycarbamate, propineb or zineb; imidazole fungicides, such as
cyazofamid, fenamidone, fenapanil, glyodin, iprodione,
isovaledione, pefurazoate or triazoxide; inorganic fungicides, such
as potassium azide, sodium azide or sulfur; morpholine fungicides,
such as, e.g., aldimorph, benzamorf, carbamorph, dimethomorph,
dodemorph, fenpropimorph, flumorph or tridemorph; organophosphorus
fungicides, such as ampropylfos, ditalimfos, edifenphos, fosetyl,
hexylthiofos, iprobenfos, phosdiphen, pyrazophos, toiclofos-methyl
or triamiphos; organotin fungicides, such as decafentin, fentin or
tributyltin oxide; oxathiin fungicides, such as carboxin or
oxycarboxin; oxazole fungicides, such as chlozolinate,
dichlozoline, drazoxolon, famoxadone, hymexazol, metazoxolon,
myclozolin, oxadixyl or vinclozolin; polysulfide fungicides, such
as barium polysulfide, potassium polysulfide or sodium polysulfide;
pyrazole fungicides, such as furametpyr or penthiopyrad; pyridine
fungicides, such as boscalid, buthiobate, dipyrithione, fluazinam,
fluopicolide, pyridinitril, pyrifenox, pyroxychloror pyroxyfur;
pyrimidine fungicides, such as bupirimate, cyprodinil,
diflumetorim, dimethirimol, ethirimol, fenarimol, ferimzone,
mepanipyrim, nuarimol, pyrimethanil or triarimol; pyrrole
fungicides, such as fenpiclonil, fludioxonil or fluoroimide;
quinoline fungicides, such as ethoxyquin, halacrinate,
8-hydroxyquinoline sulfate, quinacetol or quinoxyfen; quinone
fungicides, such as benquinox, chloranil, dichlone or dithianone;
quinoxaline fungicides, such as quinomethionate, chlorquinox or
thioquinox; thiazole fungicides, such as ethaboxam, etridiazole,
metsulfovax, octhilinone, thiabendazole, thiadifluor or
thifluzamide; thiocarbamate fungicides, such as methasulfocarb or
prothiocarb; thiophene fungicides, such as ethaboxam or silthiofam;
triazine fungicides, such as anilazine; triazole fungicides, such
as bitertanol, fluotrimazole or triazbutil; urea fungicides, such
as bentaluron, pencycuron or quinazamid; or unclassified
fungicides, such as acibenzolar, acypetacs, allyl alcohol,
benzalkonium chloride, benzamacril, bethoxazin, carvone, DBCP,
dehydroacetic acid, diclomezine, diethyl pyrocarbonate,
fenaminosulf, fenitropan, fenpropidin, formaldehyde, furfural,
hexachlorbutadiene, isoprothiolane, methyl isothiocyanate,
metrafenone, nitrostyrene, nitrothal-isopropyl, OCH, phthalide,
piperalin, probenazole, proquinazid, pyroquilon, sodium
orthophenylphenoxide, spiroxamine, sultropen, thicyofen,
tricyclazole or zinc naphthenate.
[0258] According to a particular embodiment of the invention,
fungicides (e1) comprise: [0259] 1. acylalanines, such as
benalaxyl, metalaxyl, ofurace or oxadixyl; [0260] 2. amine
derivatives, such as aldimorph, dodine, dodemorph, fenpropimorph,
fenpropidin, guazatine, iminoctadine, spiroxamine or tridemorph;
[0261] 3. anilinopyrimidines, such as pyrimethanil, mepanipyrim or
cyprodinil; [0262] 4. antibiotics, such as cycloheximide,
griseofulvin, kasugamycin, natamycin, polyoxin and streptomycin;
[0263] 5. azoles: azaconazole, bitertanol, bromoconazole,
cyproconazole, diclobutrazol, difenoconazole, diniconazole,
epoxiconazole, fenbuconazole, fluquinconazole, flusilazole,
flutriafol, ketoconazole, hexaconazole, metconazole, myclobutanil,
penconazole, propiconazole, prothioconazole, tebuconazole,
tetraconazole, triadimefon, triadimenol, triflumizole or
triticonazole; [0264] 6. dicarboximides, such as iprodione,
myclozolin, procymidone or vinclozolin; [0265] 7. dithiocarbamates:
ferbam, nabam, maneb, mancozeb, metam, metiram, propineb,
polycarbamate, thiram, ziram or zineb; [0266] 8. heterocyclic
compounds, such as anilazine, benomyl, boscalid, carbendazim,
carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone,
fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr,
isoprothiolane, mepronil, nuarimol, probenazole, proquinazid,
pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole,
thifluzamide, thiophanate-methyl, tiadinil, tricyclazole or
triforine; [0267] 9. nitrophenyl derivatives, such as binapacryl,
dinocap, dinobuton or nitrothal-isopropyl; [0268] 10.
phenylpyrroles, such as fenpiclonil and fludioxonil; [0269] 11.
2-methoxybenzophenones, such as disclosed in EP-A 897 904, e.g.
metrafenone; [0270] 12. fungicides belonging to no other class,
such as acibenzolar-5-methyl, benthiavalicarb, carpropamid,
chlorothalonil, cyflufenamid, cymoxanil, diclomezine, diclocymet,
diethofencarb, edifenphos, ethaboxam, fenhexamid, fentin acetate,
fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum,
iprovalicarb, metrafenone, pencycuron, propamocarb, phthalide,
tolclofos-methyl, quintozene or zoxamide; [0271] 13. strobilurins,
such as disclosed in WO 03/075663, e.g. azoxystrobin,
dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin,
orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;
[0272] 14. sulfonates, such as captafol, captan, dichlofluanid,
folpet or tolylfluanid; [0273] 15. cinnamamides and their analogs,
such as dimethomorph, flumetover or flumorph; [0274] 16.
6-aryl-[1,2,4]triazolo[1,5-a]pyrimidines, such as disclosed, e.g.,
in WO 98/46608, WO 99/41255 or WO 03/004465, e.g.
5-chloro-7-(4-methyl-piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tri-
azolo[1,5-a]pyrimidine,
5-chloro-7-(4-methylpiperazin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tria-
zolo[1,5-a]pyrimidine,
5-chloro-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-
-a]pyrimidine,
5-chloro-7-(piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-
-a]pyrimidine,
5-chloro-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-
-a]pyrimidine,
5-chloro-7-(isopropylamino)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-
-a]pyrimidine,
5-chloro-7-(cyclopentyl-amino)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[-
1,5-a]pyrimidine,
5-chloro-7-(2,2,2-trifluoroethylamino)-6-(2,4,6-trifluorophenyl)-[1,2,4]t-
riazolo[1,5-a]pyrimidine,
5-chloro-7-(1,1,1-trifluoroprop-2-ylamino)-6-(2,4,6-trifluorophenyl)-[1,2-
,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(3,3-dimethylbut-2-ylamino)-6-(2,4,6-trifluorophenyl)-[1,2,4]t-
riazolo[1,5-a]pyrimidine,
5-chloro-7-(cyclohexylmethyl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1-
,5-a]pyrimidine,
5-chloro-7-(cyclohexyl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]p-
yrimidine,
5-chloro-7-(2-methylbut-3-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]-
triazolo[1,5-a]pyrimidine,
5-chloro-7-(3-methylprop-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[-
1,5-a]pyrimidine,
5-chloro-7-(4-methylcyclohex-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triaz-
olo[1,5-a]pyrimidine,
5-chloro-7-(hex-3-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyri-
midine,
5-chloro-7-(2-methylbut-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tri-
azolo[1,5-a]pyrimidine,
5-chloro-7-(3-methylbut-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1-
,5-a]pyrimidine,
5-chloro-7-(1-methylprop-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[-
1,5-a]pyrimidine,
5-methyl-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tria-
zolo[1,5-a]pyrimidine,
5-methyl-7-(4-methylpiperazin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tria-
zolo[1,5-a]pyrimidine,
5-methyl-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-
-a]pyrimidine,
5-methyl-7-(piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-
-a]pyrimidine,
5-methyl-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-
-a]pyrimidine,
5-methyl-7-(isopropylamino)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-
-a]pyrimidine,
5-methyl-7-(cyclopentylamino)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1-
,5-a]pyrimidine,
5-methyl-7-(2,2,2-trifluoroethylamino)-6-(2,4,6-trifluorophenyl)-[1,2,4]t-
riazolo[1,5-a]pyrimidine,
5-methyl-7-(1,1,1-trifluoroprop-2-ylamino)-6-(2,4,6-trifluorophenyl)-[1,2-
,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(3,3-dimethylbut-2-ylamino)-6-(2,4,6-trifluorophenyl)-[1,2,4]t-
riazolo[1,5-a]pyrimidine,
5-methyl-7-(cyclohexylmethyl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1-
,5-a]pyrimidine,
5-methyl-7-(cyclohexyl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]p-
yrimidine,
5-methyl-7-(2-methylbut-3-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]-
triazolo[1,5-a]pyrimidine,
5-methyl-7-(3-methylprop-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[-
1,5-a]pyrimidine,
5-methyl-7-(4-methylcyclohex-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triaz-
olo[1,5-a]pyrimidine,
5-methyl-7-(hex-3-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyr-
imidine,
5-methyl-7-(2-methylbut-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tr-
iazolo[1,5-a]pyrimidine,
5-methyl-7-(3-methylbut-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1-
,5-a]pyrimidine and
5-methyl-7-(1-methylprop-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[-
1,5-a]pyrimidine; [0275] 17. Amide fungicides, such as
cyclofenamid, and
(Z)-N-[.alpha.-(cyclopropylmethoxyimino)-2,3-difluoro-6-(difluoromethoxy)-
benzyl]-2-phenylacetamide.
[0276] Herbicides (e2) comprise, for example, amide herbicides,
such as allidochlor, beflubutamid, benzadox, benzipram,
bromobutide, cafenstrole, CDEA, chlorthiamid, cyprazole,
dimethenamid, dimethenamid-P, diphenamid, epronaz, etnipromid,
fentrazamide, flupoxam, fomesafen, halosafen, isocarbamid,
isoxaben, napropamide, naptalam, pethoxamid, propyzamide,
quinonamid or tebutam; in particular anilide herbicides, such as
chloranocryl, cisanilide, clomeprop, cypromid, diflufenican,
etobenzanid, fenasulam, flufenacet, flufenican, mefenacet,
mefluidide, metamifop, monalide, naproanilide, pentanochlor,
picolinafen or propanil; in particular arylalanine herbicides, such
as benzoylprop, flamprop or flamprop-M; chloroacetanilide
herbicides, such as acetochlor, alachlor, butachlor, butenachlor,
delachlor, diethatyl, dimethachlor, metazachlor, metolachlor,
S-metolachlor, pretilachlor, propachlor, propisochlor, prynachlor,
terbuchlor, thenylchloror xylachlor; and sulfonanilide herbicides,
such as benzofluor, cloransulam, diclosulam, florasulam,
flumetsulam, metosulam, perfluidone, pyrimisulfan or profluazol;
and sulfonamide herbicides, such as asulam, carbasulam, fenasulam,
oryzalin or penoxsulam; antibiotic herbicides, such as bilanafos;
aromatic acid herbicides; in particular benzoate herbicides, such
as chloramben, dicamba, 2,3,6-TBA or tricamba; in particular
pyrimidinyloxybenzoate herbicides, such as bispyribac or
pyriminobac; and pyrimidinylthiobenzoate herbicides, such as
pyrithiobac; phthalate herbicides, such as chlorthal; picolinate
herbicides, such as aminopyralid, clopyralid or picloram; and
quinolinecarboxylate herbicides, such as quinclorac or quinmerac;
arsenical herbicides, such as cacodylat, CMA, DSMA, hexaflurate,
MAA, MAMA, MSMA, potassium arsenite or sodium arsenite;
benzoylcyclohexanedione herbicides, such as mesotrione or
sulcotrione; benzofuranyl alkylsulfonate herbicides, such as
benfuresate or ethofumesate; carbamate herbicides, such as asulam,
carboxazole, chlorprocarb, dichlormate, fenasulam, karbutilate or
terbucarb; carbanilate herbicides, such as barban, BCPC,
carbasulam, carbetamide, CEPC, chlorbufam, chlorpropham, CPPC,
desmedipham, phenisopham, phenmedipham, phenmedipham-ethyl, propham
or swep; cyclohexene oxime herbicides, such as alloxydim,
butroxydim, clethodim, cloproxydim, cycloxydim, profoxydim,
sethoxydim, tepraloxydim or tralkoxydim; cyclopropylisoxazole
herbicides, such as isoxachlortole or isoxaflutole; dicarboximide
herbicides, such as benzfendizone, cinidon-ethyl, flumezin,
flumiclorac, flumioxazin or flumipropyn; dinitroaniline herbicides,
such as benfluralin, butralin, dinitramine, ethalfluralin,
fluchloralin, isopropalin, methalpropalin, nitralin, oryzalin,
pendimethalin, prodiamine, profluralin or trifluralin;
dinitrophenol herbicides, such as dinofenate, dinoprop, dinosam,
dinoseb, dinoterb, DNOC, etinofen or medinoterb; diphenyl ether
herbicides, such as ethoxyfen; in particular nitrophenyl ether
herbicides, such as acifluorfen, aclonifen, bifenox,
chlomethoxyfen, chlornitrofen, etnipromid, fluorodifen,
fluoroglycofen, fluoronitrofen, fomesafen, furyloxyfen, halosafen,
lactofen, nitrofen, nitrofluorfen or oxyfluorfen; dithiocarbamate
herbicides, such as dazomet or metam; halogenated aliphatic
herbicides, such as alorac, chloropon, dalapon, flupropanate,
hexachloroacetone, chloroacetic acid, SMA or TCA; imidazolinone
herbicides, such as imazamethabenz, imazamox, imazapic, imazapyr,
imazaquin or imazethapyr; inorganic herbicides, such as ammonium
sulfamate, calcium chlorate, copper sulfate, iron sulfate,
potassium azide, potassium cyanide, sodium azide, sodium chlorate
or sulfuric acid; nitrile herbicides, such as bromobonil,
bromoxynil, chloroxynil, dichlobenil, iodobonil, ioxynil or
pyraclonil; organophosphorus herbicides, such as amiprofosmethyl,
anilofos, bensulide, bilanafos, butamifos, 2,4-DEP, DMPA, EBEP,
fosamine, glufosinate, glyphosate or piperophos; phenoxy
herbicides, such as bromofenoxim, clomeprop, 2,4-DEB, 2,4-DEP,
difenopenten, disul, erbon, etnipromid, fenteracol or trifopsime;
in particular phenoxyacetic acid herbicides, such as 4-CPA, 2,4-D,
3,4-DA, MCPA or MCPA-thioethyl; phenoxybutyric acid herbicides,
such as 4-CPB, 2,4-DB, 3,4-DB, MCPB or 2,4,5-TB; and
phenoxypropionic acid herbicides, such as cloprop, 4-CPP,
dichlorprop, dichlorprop-P, 3,4-DP, fenoprop, mecoprop or
mecoprop-P; in particular aryloxyphenoxypropionic acid herbicides,
such as chlorazifop, clodinafop, clofop, cyhalofop, diclofop,
fenoxaprop, fenoxaprop-P, fenthiaprop, fluazifop, fluazifop-P,
haloxyfop, haloxyfop-P, isoxapyrifop, metamifop, propaquizafop,
quizalofop, quizalofop-P or trifop; phenylenediamine herbicides,
such as dinitramine or prodiamine; phenyl pyrazolyl ketone
herbicides, such as benzofenap, pyrazolynate, pyrazoxyfen or
topramezone; pyrazolylphenyl herbicides, such as fluazolate or
pyraflufen; pyridazine herbicides, such as credazine, pyridafol or
pyridate; pyridazinone herbicides, such as brompyrazon,
chloridazon, dimidazon, flufenpyr, metflurazon, norflurazon,
oxapyrazon or pydanon; pyridine herbicides, such as aminopyralid,
cliodinate, clopyralid, dithiopyr, fluoroxypyr, haloxydine,
picloram, picolinafen, pyriclor, thiazopyr or triclopyr;
pyrimidinediamine herbicides, such as iprymidam or tioclorim;
quarternary ammonium herbicides, such as cyperquat, diethamquat,
difenzoquat, diquat, morfamquat or paraquat; thiocarbamate
herbicides, such as butylate, cycloate, di-allate, EPTC, esprocarb,
ethiolate, isopolinate, methiobencarb, molinate, orbencarb,
pebulate, prosulfocarb, pyributicarb, sulfallate, thiobencarb,
tiocarbazil, tri-allate or vernolate; thiocarbonate herbicides,
such as dimexano, EXD or proxane; thiourea herbicides, such as
methiuron; triazine herbicides, such as dipropetryn, triaziflam or
trihydroxytriazine; in particular chlorotriazine herbicides, such
as atrazine, chlorazine, cyanazine, cyprazine, eglinazine, ipazine,
mesoprazine, procyazine, proglinazine, propazine, sebuthylazine,
simazine, terbuthylazine or trietazine; methoxytriazine herbicides,
such as atraton, methometon, prometon, secbumeton, simeton or
terbumeton; and methylthiotriazine herbicides, such as ametryn,
aziprotryne, cyanatryn, desmetryn, dimethametryn, methoprotryne,
prometryn, simetryn or terbutryn; triazinone herbicides, such as
ametridione, amibuzin, hexazinone, isomethiozin, metamitron or
metribuzin; triazole herbicides, such as amitrole, cafenstrole,
epronaz or flupoxam; triazolone herbicides, such as amicarbazone,
carfentrazone, flucarbazone, propoxycarbazone or sulfentrazone;
triazolopyrimidine herbicides, such as cloransulam, diclosulam,
florasulam, flumetsulam, metosulam or penoxsulam; uracil
herbicides, such as butafenacil, bromacil, flupropacil, isocil,
lenacil or terbacil; urea herbicides, such as benzthiazuron,
cumyluron, cycluron, dichloralurea, diflufenzopyr, isonoruron,
isouron, methabenzthiazuron, monisouron or noruron; in particular
phenylurea herbicides, such as anisuron, buturon, chlorbromuron,
chloreturon, chlorotoluron, chloroxuron, daimuron, difenoxuron,
dimefuron, diuron, fenuron, fluometuron, fluothiuron, isoproturon,
linuron, methiuron, methyldymron, metobenzuron, metobromuron,
metoxuron, monolinuron, monuron, neburon, parafluoron,
phenobenzuron, siduron, tetrafluoron or thidiazuron; sulfonylurea
herbicides; in particular pyrimidinylsulfonylurea herbicides, such
as amidosulfuron, azimsulfuron, bensulfuron, chlorimuron,
cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron,
flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron,
mesosulfuron, nicosulfuron, orthosulfamuron, oxasulfuron,
primisulfuron, pyrazosulfuron, rimsulfuron, sulfometuron,
sulfosulfuron or trifloxysulfuron; and triazinylsulfonylurea
herbicides, such as chlorsulfuron, cinosulfuron, ethametsulfuron,
iodosulfuron, metsulfuron, prosulfuron, thifensulfuron,
triasulfuron, tribenuron, triflusulfuron or tritosulfuron; and
thiadiazolylurea herbicides, such as buthiuron, ethidimuron,
tebuthiuron, thiazafluoron or thidiazuron; and other herbicides,
such as acrolein, allyl alcohol, azafenidin, benazolin, bentazone,
benzobicyclon, buthidazole, calcium cyanamide, cambendichlor,
chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol,
cinmethylin, clomazone, CPMF, cresol, ortho-dichlorobenzene,
dimepiperate, endothal, fluoromidine, fluridone, fluorochloridone,
flurtamone, fluthiacet, indanofan, methazole, methyl
isothiocyanate, nipyraclofen, OCH, oxadiargyl, oxadiazon,
oxaziclomefone, pentoxazone, pinoxaden, prosulfalin, pyribenzoxim,
pyriftalid, quinoclamine, rhodethanil, sulglycapin, thidiazimin,
tridiphane, trimeturon, tripropindan or tritac.
[0277] According to a particular embodiment of the invention,
herbicides (e2) comprise: [0278] 1. 1,3,4-thiadiazoles, such as
buthidazole and cyprazole; [0279] 2. amides, such as allidochlor,
benzoylprop-ethyl, bromobutide, chlorthiamid, dimepiperate,
dimethenamid, diphenamid, etobenzanid, flamprop, flampropmethyl,
fosamine, isoxaben, metazachlor, monalide, naptalam, pronamide,
propanil, propyzamide or quinonamid; [0280] 3. aminotriazoles, such
as amitrole, [0281] 4. anilides, such as anilofos, mefenacet or
pentanochlor; [0282] 5. aryloxycarboxylic acids, such as 2,4-D,
2,4-DB, clomeprop, dichlorprop, dichlorprop-P, fenoprop,
fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide,
naproanilide or triclopyr; [0283] 6. benzoic acids, such as
chloramben or dicamba; [0284] 7. benzothiadiazinones, such as
bentazon; [0285] 8. bleachers, such as clomazone, diflufenican,
fluorochloridone, flupoxam, fluridone, karbutilate, pyrazolate,
sulcotrione or mesotrione; [0286] 9. carbamates, such as asulam,
carbetamide, chlorbufam, chlorpropham, desmedipham, phenmedipham or
vernolate; [0287] 10. quinolates, such as quinclorac or quinmerac;
[0288] 11. dichloropropionic acids, such as dalapon; [0289] 12.
dihydrobenzofurans, such as ethofumesate; [0290] 13.
dihydrofuran-3-ones, such as flurtamone; [0291] 14.
dinitroanilines, such as benefin, butralin, dinitramine,
ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin,
pendimethalin, prodiamine, profluralin or trifluralin; [0292] 15.
dinitrophenols, such as bromofenoxim, dinoseb, dinoseb acetate,
dinoterb, DNOC or minoterb-acetate; [0293] 16. diphenyl ethers,
such as acifluorfen, acifluorfen-sodium, aclonifen, bifenox,
chlornitrofen, difenoxuron, ethoxyfen, fluorodifen,
fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen,
nitrofluorfen or oxyfluorfen; [0294] 17. ureas, such as
benzthiazuron, DCU, diflufenzopyr or methabenzthiazuron; [0295] 18.
imidazolinones, such as imazamethapyr, imazapyr, imazaquin,
imazethabenzmethyl, imazethapyr, imazapic or imazamox; [0296] 19.
oxadiazoles, such as methazole, oxadiargyl, oxadiazon; [0297] 20.
oxiranes, such as tridiphane; [0298] 21. phenols, such as
bromoxynil or ioxynil; [0299] 22. phenoxyphenoxypropionic acid
esters, such as clodinafop, cyhalofop-butyl, diclofop-methyl,
fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenthiaprop-ethyl,
fluazifop-butyl, fluazifop-P-butyl, haloxyfop-ethoxyethyl,
haloxyfop-methyl, haloxyfop-P-methyl, isoxapyrifop, propaquizafop,
quizalofop-ethyl, quizalofop-P-ethyl or quizalofop-tefuryl; [0300]
23. phenylacetic acids, such as chlorfenac; [0301] 24. phenylureas,
such as buturon, chlorotoluron, chlorbromuron, chloroxuron,
dimefuron, diuron, fenuron, isoproturon, linuron, monolinuron,
monuron, metobenzuron, metobromuron, metoxuron or neburon; [0302]
25. phenylpropionic acids, such as chlorfenprop-methyl; [0303] 26.
Ppi-active compounds, such as benzofenap, flumiclorac,
flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil,
pyrazoxyfen, sulfentrazone or thidiazimin; [0304] 27. pyrazoles,
such as nipyraclofen; [0305] 28. pyridazines, such as chloridazon,
maleic hydrazide, norflurazon or pyridate; [0306] 29.
pyridinecarboxylates, such as clopyralid, dithiopyr, picloram or
thiazopyr; [0307] 30. pyrimidyl ethers, such as pyrithiobac,
pyrithiobac-sodium, KIH-2023 or KIH-6127; [0308] 31. sulfonamides,
such as flumetsulam or metosulam; [0309] 32. sulfonylureas, such as
amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl,
chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron,
ethametsulfuron-methyl, flazasulfuron, flupyrsulfuron-methyl,
foramsulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron,
metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron,
prosulfuron, pyrazosulfuron-ethyl, rimsulfuron,
sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl,
triasulfuron, tribenuron-methyl, triflusulfuron-methyl or
tritosulfuron; [0310] 33. thiadiazolylureas, such as ethidimuron,
tebuthiuron or thiazafluoron; [0311] 34. triazines, such as
ametryn, atrazine, atraton, cyanazine, cyprazine, desmetryn,
dipropetryn, isomethiozin, propazine, prometryn, prometon,
sebuthylazine, secbumeton, simazine, terbutryn, terbumeton,
terbuthylazine or trietazine; [0312] 35. triazolecarboxamides, such
as triazofenamide; [0313] 36. uracils, such as bromacil,
butafenacil, lenacil or terbacil; [0314] 37. furthermore
azafenidin, aziprotryn, bromuron, benazolin, benfuresate,
bensulide, benzofluor, bentazon, bromofenoxim, butamifos,
cafenstrole, chlorthal-dimethyl, cinmethylin, cinidon-ethyl,
defenuron, dichlobenil, endothall, fluorbentranil,
fluthiacet-methyl, inxynil, isoxaflutole, mefluidide, methazole,
metribuzin, metramitron, perfluidone, piperophos or topramezone;
[0315] 38. plant protection agents of the cyclohexenone type, such
as alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim and
tralkoxydim.
[0316] Particularly preferred plant protection agents of the
cyclohexanone type comprise tepraloxydim (cf. AGROW, No. 243,
11.3.95, p. 21, caloxydim) and
2-(1-[2-{4-chlorophenoxy}propyloxyimino]butyl)-3-hydroxy-5-(2H-tetrahydro-
thiopyran-3-yl)-2-cyclohexen-1-one, and a particularly preferred
herbicidally active compound of the sulfonylurea type is
N-(((4-methoxy-6-[trifluoromethyl]-1,3,5-triazin-2-yl)amino)-carbonyl)-2--
(trifluoromethyl)benzenesulfonamide.
[0317] Insecticides (e3) comprise, for example, antibiotic
insecticides, such as allosamidin or thuringiensin; in particular
macrocyclic lactone insecticides, such as spinosad; in particular
avermectin insecticides, such as abamectin, doramectin, emamectin,
eprinomectin, ivermectin or selamectin; and milbemycin
insecticides, such as lepimectin, milbemectin, milbemycinoxime or
moxidectin; arsenical insecticides, such as calcium arsenate,
copper acetoarsenite, copper arsenate, lead arsenate, potassium
arsenite or sodium arsenite; botanical insecticides, such as
anabasine, azadirachtin, d-limonene, nicotine, pyrethrins, cinerin
E, cinerin I, cinerin II, jasmolin I, jasmolin II, pyrethrin I,
pyrethrin II, quassia, rotenone, ryania or sabadilla; carbamate
insecticides, such as bendiocarb or carbaryl; in particular
benzofuranyl methylcarbamate insecticides, such as benfuracarb,
carbofuran, carbosulfan, decarbofuran or furathiocarb;
dimethylcarbamate insecticides, such as dimetan, dimetilan,
hyquincarb or pirimicarb; oxime carbamate insecticides, such as
alanycarb, aldicarb, aldoxycarb, butocarboxim, butoxycarboxim,
methomyl, nitrilacarb, oxamyl, tazimcarb, thiocarboxime, thiodicarb
or thiofanox; and phenyl methylcarbamate insecticides, such as
allyxycarb, aminocarb, bufencarb, butacarb, carbanolate,
cloethocarb, dicresyl, dioxacarb, EMPC, ethiofencarb, fenethacarb,
fenobucarb, isoprocarb, methiocarb, metolcarb, mexacarbate,
promacyl, promecarb, propoxur, trimethacarb, XMC or xylylcarb;
dinitrophenol insecticides, such as dinex, dinoprop, dinosam or
DNOC; insect growth regulators; in particular chitin synthesis
inhibitors, such as bistrifluoron, buprofezin, chlorfluazuron,
cyromazine, diflubenzuron, flucycloxuron, flufenoxuron,
hexaflumuron, lufenuron, novaluron, noviflumuron, penfluoron,
teflubenzuron or triflumuron; juvenile hormone mimics, such as
epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene,
pyriproxyfen or triprene; juvenile hormones, such as juvenile
hormone I, II and III; moulting hormone agonists, such as
chromafenozide, halofenozide, methoxyfenozide, tebufenozide;
moulting hormones, such as .alpha.-ecdysone or ecdysterone;
moulting inhibitors, such as diofenolan; precocenes, such as
precocene I, II and III; and unclassified insecticides, such as
dicyclanil; nereistoxin analogs, such as bensultap, cartap,
thiocyclam or thiosultap; nicotinoid insecticides, such as
flonicamid; in particular nitroguanidine insecticides, such as
clothianidin, dinotefuran, imidacloprid or thiamethoxam;
nitromethylene insecticides, such as nitenpyram or nithiazine; and
pyridylmethylamine insecticides, such as acetamiprid, imidacloprid,
nitenpyram or thiacloprid; organochlorine insecticides, such as
isobenzan, isodrin, kelevan or mirex; organophosphorus
insecticides, in particular organophosphate insecticides, such as
bromfenvinfos, chlorfenvinphos, crotoxyphos, dichlorvos,
dicrotophos, dimethylvinphos, fospirate, heptenophos,
methocrotophos, mevinphos, monocrotophos, naled, naftalofos,
phosphamidon, propaphos, TEPP or tetrachlorvinphos;
organothiophosphate insecticides, such as dioxabenzofos,
fosmethilan or phenthoate; in particular aliphatic
organothiophosphate insecticides, such as acethion, amiton,
cadusafos, chlorethoxyfos, chlormephos, demephion, demephion-O,
demephion-S, demeton, demeton-O, demeton-S, demeton-methyl,
demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon,
disulfoton, ethion, ethoprophos, IPSP, isothioate, malathion,
methacrifos, oxydemeton-methyl, oxydeprofos, oxydisulfoton,
phorate, sulfotep, terbufos or thiometon; in particular aliphatic
amide organothiophosphate insecticides, such as amidithion,
cyanthoate, dimethoate, ethoate-methyl, formothion, mecarbam,
omethoate, prothoate, sophamide or vamidothion; and oxime
organothiophosphate insecticides, such as chlorphoxim, phoxim or
phoxim-methyl; heterocyclic organothiophosphate insecticides, such
as azamethiphos, coumaphos, coumithoate, dioxathion, endothion,
menazon, morphothion, phosalone, pyraclofos, pyridaphenthion or
quinothion; especially benzothiopyran organothiophosphate
insecticides, such as dithicrofos or thicrofos; benzotriazine
organothiophosphate insecticides, such as azinphos-ethyl or
azinphos-methyl; isoindole organothiophosphate insecticides, such
as dialifos or phosmet; isoxazole organothiophosphate insecticides,
such as isoxathion or zolaprofos; pyrazolopyrimidine
organothiophosphate insecticides, such as chlorprazophos or
pyrazophos; pyridine organothiophosphate insecticides, such as
chlorpyrifos or chlorpyrifos-methyl; pyrimidine organothiophosphate
insecticides, such as butathiofos, diazinon, etrimfos, lirimfos,
pirimiphos-ethyl, pirimiphos-methyl, primidophos, pyrimitate or
tebupirimfos; quinoxaline organothiophosphate insecticides, such as
quinalphos or quinalphosmethyl; thiadiazole organothiophosphate
insecticides, such as athidathion, lythidathion, methidathion or
prothidathion; and triazole organothiophosphate insecticides, such
as isazofos or triazophos; and phenyl organothiophosphate
insecticides, such as azothoate, bromophos, bromophos-ethyl,
carbophenothion, chlorthiophos, cyanophos, cythioate, dicapthon,
dichlofenthion, etaphos, famphur, fenchlorphos, fenitrothion,
fensulfothion, fenthion, fenthion-ethyl, heterophos, jodfenphos,
mesulfenfos, parathion, parathion-methyl, phenkapton, phosnichlor,
profenofos, prothiofos, sulprofos, temephos, trichlormetaphos-3 or
trifenofos; phosphonate insecticides, such as butonate or
trichlorfon; phosphonothioate insecticides, such as mecarphon; in
particular phenyl ethylphosphonothioate insecticides, such as
fonofos or trichloronat; and phenyl phenylphosphonothioate
insecticides, such as cyanofenphos, EPN or leptophos;
phosphoramidate insecticides, such as crufomate, fenamiphos,
fosthietan, mephosfolan, phosfolan or pirimetaphos;
phosphoramidothioate insecticides, such as acephate, isocarbophos,
isofenphos, methamidophos and propetamphos; and phosphorodiamide
insecticides, such as dimefox, mazidox, mipafox or schradan;
oxadiazine insecticides, such as indoxacarb; phthalimide
insecticides, such as dialifos, phosmet or tetramethrin; pyrazole
insecticides, such as acetoprole, ethiprole, fipronil,
pyrafluprole, pyriprole, tebufenpyrad, tolfenpyrad or vaniliprole;
pyrethroid insecticides; in particular pyrethroid ester
insecticides, such as acrinathrin, allethrin, bioallethrin,
barthrin, bifenthrin, bioethanomethrin, cyclethrin, cycloprothrin,
cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin,
lambda-cyhalothrin, cypermethrin, alphacypermethrin,
beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin,
cyphenothrin, deltamethrin, dimefluthrin, dimethrin, empenthrin,
fenfluthrin, fenpirithrin, fenpropathrin, fenvalerate,
esfenvalerate, flucythrinate, fluvalinate, tau-fluvalinate,
furethrin, imiprothrin, metofluthrin, permethrin, biopermethrin,
transpermethrin, phenothrin, prallethrin, profluthrin,
pyresmethrin, resmethrin, bioresmethrin, cismethrin, tefluthrin,
terallethrin, tetramethrin, tralomethrin or transfluthrin; and
pyrethroid ether insecticides, such as etofenprox, flufenprox,
halfenprox, protrifenbute or silafluofen; pyrimidinamine
insecticides, such as flufenerim or pyrimidifen; pyrrole
insecticides, such as chlorfenapyr; tetronic acid insecticides,
such as spiromesifen; thiourea insecticides, such as diafenthiuron;
urea insecticides, such as flucofuron or sulcofuron; or
unclassified insecticides, such as closantel, crotamiton, EXD,
fenazaflor, fenoxacrim, flubendiamide, hydramethylnon,
isoprothiolane, malonoben, metaflumizone, metoxadiazone,
nifluridide, pyridaben, pyridalyl, rafoxanide, triarathene or
triazamate.
[0318] According to a particular embodiment of the present
invention, insecticides (e3) comprise: [0319] 1. organophosphates,
such as azinphos-methyl, azinphos-ethyl, chlorpyrifos,
chlorpyrifos-methyl, chlorfenvinphos, diazinon, dimethylvinphos,
dioxabenzofos, disulfoton, ethion, EPN, fenitrothion, fenthion,
heptenophos, isoxathion, malathion, methidathion, methyl parathion,
paraoxon, parathion, phenthoate, phosalone, phosmet, phorate,
phoxim, pirimiphos-methyl, profenofos, prothiofos,
pirimiphos-ethyl, pyraclofos, pyridaphenthion, sulprofos,
triazophos, trichlorfon, tetrachlorvinphos or vamidothion; [0320]
2. carbamates, such as alanycarb, benfuracarb, bendiocarb,
carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb,
indoxacarb, methiocarb, pirimicarb, propoxur, thiodicarb or
triazamate; [0321] 3. pyrethroids, such as bifenthrin, cyfluthrin,
cycloprothrin, cypermethrin, deltamethrin, esfenvalerate,
etofenprox, fenpropathrin, fenvalerate, cyhalothrin,
lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate,
tefluthrin, tralomethrin or alpha-cypermethrin; [0322] 4. arthropod
growth regulators: [0323] A) chitin synthesis inhibitors, e.g.
benzoylureas, such as chlorfluazuron, diflubenzuron, flucycloxuron,
flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron,
triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole or
clofentezine; [0324] B) ecdysone antagonists, such as halofenozide,
methoxyfenozide or tebufenozide; [0325] C) juvenile hormone mimics,
such as pyriproxyfen or methoprene; [0326] D) lipid biosynthesis
inhibitors, such as spirodiclofen; [0327] 5. neonicotinoids, such
as flonicamid, clothianidin, dinotefuran, imidacloprid,
thiamethoxam, nithiazine, acetamiprid or thiacloprid; [0328] 6.
additional insecticides which cannot be assigned to any of the
abovementioned classes, such as abamectin, acequinocyl,
acetamiprid, azadirachtin, bensultap, bifenazate, cartap,
chlorfenapyr, diafenthiuron, dinotefuran, diofenolan, emamectin,
ethiprole, fenazaquin, fipronil, hydramethylnon, imidacloprid,
indoxacarb, isoprocarb, metolcarb, pyridaben, pymetrozine,
spinosad, tebufenpyrad, thiamethoxam, XMC and xylylcarb, and [0329]
7. N-phenylsemicarbazones, such as disclosed in EP-A 462 456, in
particular compounds of the general formula (IV)
[0329] ##STR00010## [0330] in which R.sup.12 and R.sup.14 can,
independently of one another, be hydrogen, halogen, CN,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-4-haloalkyl
or C.sub.1-4-haloalkoxy and R.sup.13 is C.sub.1-4-alkoxy,
C.sub.1-4-haloalkyl or C.sub.1-4-haloalkoxy, e.g. compounds
according to formula (IV) in which R.sup.14=3-CF.sub.3,
R.sup.12=4-CN and R.sup.13=4-OCF.sub.3.
[0331] Salts, in particular agriculturally useful salts, of the
active agents especially mentioned here can also be used.
[0332] In a particular embodiment of the invention, the plant
protection active agent is a fungicide.
[0333] In this context, it is particularly preferable for the
fungicide to be an active agent from the group consisting of the
strobilurins and triazoles, in particular a strobilurin chosen from
azoxystrobin, pyraclostrobin, dimoxystrobin, trifloxystrobin,
fluoxastrobin, picoxystrobin and orysastrobin or a triazole chosen
from epoxiconazole, metconazole, tebuconazole, flusilazole,
fluquinconazole, triticonazole, propiconazole, penconazole,
cyproconazole and prothioconazole.
[0334] The use of epoxiconazole is particularly preferred according
to the invention.
[0335] The names of plant protection active agents, e.g.
epoxiconazole, chosen here include isomeric forms of these
compounds. Mention may be made in particular of stereoisomers, such
as enantiomers or diastereomers, of the formulae. In addition to
the essentially pure isomers, the compounds of the formulae also
include their isomeric mixtures, e.g. stereoisomeric mixtures.
[0336] Preference is generally given to active agents with a higher
proportion of the stereoisomer which, with regard to the optical
antipode, is biologically more active, particularly preferably
isomerically pure active agents.
[0337] The proportion of the active agent component (e) in the
total weight of the composition generally comes to more than 1% by
weight, preferably more than 2% by weight and in particular more
than 2.5% by weight. On the other hand, the proportion of the
component (e) in the total weight of the composition generally
comes to less than 50% by weight, preferably less than 40% by
weight and in particular less than 35% by weight, based on the
total weight of the composition.
[0338] In a particular embodiment of the invention, the composition
is essentially anhydrous, in particular with a water content of
less than 5% and especially of less than 2% of the total
weight.
[0339] In a particular embodiment of the invention, the composition
is of low hygroscopicity, it being preferable for its moisture
absorption at 65% atmospheric humidity to be less than 20% by
weight, preferably less than 15% by weight and particularly
preferably less than 10% by weight.
[0340] In a particular embodiment of the invention, the composition
is a particulate solid, in particular a granule or powder.
[0341] In this context, it is particularly preferable for the
granule to be coarse-grained.
[0342] In this context, it is furthermore particularly preferable
for the granule to be chosen from water-dispersible granules (WG)
and water-soluble granules (SG), it being possible in particular
for fluidized bed granules (FBG) to be concerned in this
context.
[0343] In addition, it is particularly preferable for the powder to
be a dry flowable (DF) powder, in particular a powder capable of
being poured or trickled, particularly preferably again a powder
with a particle size ranging from 1 to 200 .mu.m, preferably
ranging from 2 to 150 .mu.m and in particular ranging from 5 to 100
.mu.m, determined according to the CIPAC MT 59 method ("dry sieve
test").
[0344] In a particular embodiment of the invention, the composition
is essentially dust-free, determined according to the CIPAC MT 171
method ("dustiness of granular formulations").
[0345] In a particular embodiment of the invention, the composition
is essentially stable on storage; in particular, it does not
agglutinate on storage; in particular, it does not agglutinate on
storage for at least eight weeks, preferably on storage for at
least 12 weeks, at a temperature ranging from -10.degree. C. to
40.degree. C., determined according to the CIPAC MT 172 method
("flowability of water").
[0346] In a particular embodiment of the invention, the composition
is dispersable in water, determined according to the CIPAC MT 174
method ("dispersibility of water dispersible granules").
[0347] An additional subject matter of the present invention is a
process for the preparation of a solid plant protection composition
according to the invention.
[0348] In this context,
[0349] FIG. 1 shows a diagrammatic representation of possible
preparation routes.
[0350] In the practical preparation of the plant protection
compositions according to the invention, use is generally made of
commercial products which may yet additionally comprise solvents,
for example water, and other additives, preferably high
concentrates being used. In particular, relatively small amounts of
inorganic substances, especially inorganic salts, may be included
in the products used. Thus, relatively high molecular weight
sulfonates may comprise, as a result of the preparation, up to 20%
by weight of inorganic salts, in particular inorganic alkali metal
salts, e.g. sodium sulfate. All amounts, such as percentages by
weight and ratios by weight, in particular for the polyalkoxylates
and relatively high molecular weight sulfonates according to the
invention, are based according to the invention on the constituents
mentioned by name and are to be converted on use of such commercial
products in accordance with the actual content in the product of
the constituents mentioned.
[0351] The solid plant protection composition can be prepared
according to the invention by removing fluid from a
fluid-comprising mixture comprising at least a portion of the
ingredients and obtaining the solid at least partially freed from
the fluid. The usual ingredients can, if need be, be introduced
before removal of the fluid and/or can be added after removal of
the fluid. In this context, the initial charge preferably ensues as
solid. The admixture can ensue as fluid-comprising mixture, after
which fluid is once again removed and the solid is obtained at
least partially freed from the fluid. The fluid is preferably a
solvent for one or more ingredients, in particular water. In the
course of a multistage process, different fluids can also be
used.
[0352] In a preferred embodiment, the fluid-comprising mixture
comprises at least a portion of the components (a) and (b).
Generally, it is even advisable for such a fluid-comprising mixture
to comprise the total amount of the components (a) and (b).
According to an additional preferred embodiment, the
fluid-comprising mixture comprises at least a portion of the
component (e). Generally, it is even advisable for such a
fluid-comprising mixture to comprise the total amount of the
component (e).
[0353] For the preparation of the solid plant protection
compositions according to the invention, it is possible in
principle to proceed such that (i) fluid is removed from a
fluid-comprising mixture comprising components (a), (b) and (e);
(ii) a solid comprising components (a) and (b), e.g. a solid
comprising components (a) and (b) at least partially freed
beforehand from the fluid, is introduced, a fluid-comprising
mixture comprising component (e) is added and fluid is removed; or
(iii) a solid comprising component (e), e.g. a solid comprising
component (e) at least partially freed beforehand from the fluid,
is introduced, a fluid-comprising mixture comprising components (a)
and (b) is added and fluid is removed.
[0354] A solid comprising components (a) and (b) can be obtained,
for example, by removing fluid from a fluid-comprising mixture
comprising at least a portion of the components (a) and (b) and
obtaining the solid at least partially freed from the fluid.
[0355] Preference is given, as solid comprising component (e), to
powders or granules comprising at least 5% by weight, preferably at
least 10% by weight and in particular at least 15% by weight of
plant protection active agent. Such solids can be obtained, for
example, by removing fluid from a fluid-comprising mixture
comprising at least a portion of the component (e) and obtaining
the solid at least partially freed from the fluid. In addition,
mention may be made in this context in particular of common solid
formulations of plant protection active agents, for example SGs,
WGs, DFs or FBGs.
[0356] Preference is given, as fluid-comprising mixture at least of
a portion of the component (e), to concentrates comprising at least
5% by weight, preferably at least 10% by weight and in particular
at least 15% by weight of plant protection active agent. Mention
may be made, in this context, in particular of common liquid
formulations of plant protection active agents. Particular
preference is given to the use of a liquid concentrate, in
particular a single-phase concentrate, a multiphase concentrate, a
suspension concentrate (SC) or a concentrate in the form of a
suspoemulsion (SE). Furthermore, the addition is carried out
particularly preferably by spraying, in particular in the
fluidized-bed process, or by drum coating.
[0357] According to the invention, the composition is preferably
prepared by the fastest possible removal of the fluid and thus in
particular by the fastest possible drying, the processes which can
be used being known in principle from the state of the art. The
removal of fluid is described subsequently as "drying". In this
context, what matters is that the removal of the fluid on local
(molecular to supermolecular) size scales takes place quickly
enough, which is beneficial to the formation of the solids
according to the invention. The process as a whole can, on the
other hand, if the feed materials optionally used allow this and
practical considerations let this appear desirable, be carried out
comparatively slowly, e.g. by sequential application of a
relatively large number of very thin layers in the fluidized bed
process, each of which for itself is quickly dried.
[0358] Fluid should according to the invention be withdrawn up to
the or slightly above the point at which solids according to the
invention are produced. A considerably more extensive removal of
the fluid is possible in principle but not always advisable since
an excessively low residual moisture content can, according to
experience, harm the mechanical stability and dissolution
properties of many granules ("destructive drying"); without being
restricted to the theory, it is in this context assumed in
principle that excessively great drying can result in undesirable
rearrangement and crosslinking reactions in the granule. The ideal
degree of drying for a particular process product is, because of
the complexity of the system, dependent on many factors (including
the properties desired and the use intended for the granule, the
composition of the material charged, in the practical
implementation of most favorable process variables, and the like)
and is to be determined largely empirically.
[0359] According to a preferred embodiment of the invention, the
removal of the fluid is carried out by convection drying. In this
context, preference is given to processes in which the material to
be dried is sprayed in fluid or pasty condition. This includes in
particular spray drying, in which a fluid-comprising material is
sprayed (feedstock), fluid is removed in the gas stream and the
material, partially or completely freed from the fluid, is obtained
as particulate outlet product. The spray processes also include
fluidized-bed processes, in which a solid, preferably particulate,
material is introduced ("initial charge"), a fluid-comprising
material is sprayed ("feedstock"), fluid is removed in the gas
stream, by which introduced particulate material and sprayed
material are combined with one another, and the material, partially
or completely freed from the fluid, is obtained in combination with
the introduced particulate material as particulate "outlet
product".
[0360] An additional suitable drying process is freeze drying
(process C). This process is also familiar to a person skilled in
the art.
[0361] The respective process product, generally the outlet
product, can be used immediately according to the invention or, for
its part, can be used as initial charge in additional processing
stages for the preparation of the respective application form.
[0362] In a particular embodiment of the invention, the drying is
carried out by spray drying, e.g. by use of a "spray tower"
(process A).
[0363] In a specific embodiment of process A, compositions
according to the invention, e.g. water-soluble granules (SGs), are
prepared from the components (a), (b) and, if appropriate, (c) by
spray-drying suitable fluid-comprising mixtures of (a), (b) and, if
appropriate, (c), e.g. aqueous concentrates (process A1). In this
context, the discharging of product is preferably carried out
continuously.
[0364] In an additional specific embodiment of process A,
compositions according to the invention, e.g. water-soluble
granules (SGs) or dry flowable granules (DFs), are prepared from
the components (a), (b) and, if appropriate, (c), as well as (e),
by spray-drying fluid-comprising mixtures (of, e.g., aqueous
concentrates) comprising (a), (b) and, if appropriate, (c), as well
as (e) (process A2), the component (e) preferably being used in the
form of concentrates, e.g. SL, SC or SE concentrates. In this
context, the discharging of product is preferably carried out
continuously.
[0365] If a component (b2) is used, this can thus be added
technically as slurry or dispersion to the mixtures of the
components (a), (b1) and, if appropriate, (c) before the spray
drying ("co-spray-drying").
[0366] Ingredients which are assigned to the component (d) are in
many cases introduced together with the standard components, for
example in the form of commercial products.
[0367] In an additional particular embodiment of the invention, the
drying is carried out in the fluidized bed process (process B).
[0368] In the fluidized bed process, the discharging of product is
preferably carried out batchwise (batch process). For application
of the process, it is generally necessary to introduce a suitable
particulate material (carrier nuclei) by which the actual feedstock
can then be taken up during the process. The feedstock can result
from single- or multistream nozzle technology and/or bottom
nozzles. Depending on installation for and control of the process,
a single, a few or many layers can be applied to the nuclei, it
being taken into account that each individual layer should dry
quickly enough for the formation of the solids according to the
invention to be beneficial. The choice of the number and
thicknesses of the layers is, because of the complexity of the
system, dependent on many factors (including, e.g., desired
properties and use of the granule, composition of the material
charged, in the practical implementation of most favorable process
variables, and the like) and is to be determined largely
empirically.
[0369] In a specific embodiment of process B, compositions
according to the invention, e.g. water-soluble granules (SGs), are
prepared by introducing particulate material (carrier nuclei) based
on the component (d) and charging fluid-comprising mixtures (e.g.
aqueous concentrates) comprising components (a), (b) and, if
appropriate, (c) (process B1).
[0370] In an additional specific embodiment of process B,
compositions according to the invention, in particular WGs, SGs or
DFs, are prepared by introducing at least one solid comprising the
components (a), (b) and, if appropriate, (c), generally a
particulate solid, and subsequently charging one or more
fluid-comprising mixtures (preferably in the form of concentrates,
e.g. SL, SC or SE concentrates) comprising the component (e) and,
if appropriate, additional portions of (c) (process B2). For the
introduction of the initial charge, suitable particles can be
prepared beforehand, e.g. by one of the processes A1, B1 or C.
[0371] In a particular embodiment of process B2, carrier nuclei
based on the component (d) are introduced so that the material
introduced comprises at least the components (a), (b), (d) and, if
appropriate, (c).
[0372] In an additional specific embodiment of process B,
compositions according to the invention, in particular WGs, SGs or
DFs, are prepared by introducing carrier nuclei based on the
component (d) and subsequently charging one or more
fluid-comprising mixtures (e.g. aqueous concentrates) comprising at
least the components (a), (b), (e) and/or, if appropriate, (c)
(process B3).
[0373] In an additional specific embodiment of process B,
compositions according to the invention, in particular WGs, SGs or
DFs, are prepared by introducing a solid with effective plant
protection activity, i.e. a solid comprising at least the component
(e) and, if appropriate, (c), in particular a granule, e.g.
available as outlet product from process B2, and charging one or
more fluid-comprising mixtures (e.g. aqueous concentrates)
comprising at least the components (a) and (b) and, if appropriate,
additional portions of (c) (process B4).
[0374] Possible connections between the individual process
sequences of the preferred embodiments of processes A and B are
represented, for example, in FIG. 1. Of course, other processes,
e.g. C, can also serve as source for the particles introduced,
e.g., in process B2. If desired, more complex sequences than those
represented in the general view are also possible (e.g. coating of
particles comprising carrier and active agent, prepared according
to A2, with an additional layer, likewise comprising carrier and
active agent, in B2), which may be suitable, e.g., for the
preparation of a combination of several active agents which are
poorly compatible with one another (e.g. different strongly acidic
and strongly basic substances or substances which can potentially
react with one another) and/or for granules with specific
properties (e.g. an extent of storage stability under extreme
climatic conditions beyond that according to the present
invention).
[0375] In this way, solid plant protection compositions, in
particular coarse plant protection composition granules, are
obtained which can be dispersed (water-dispersible granules) or
dissolved (water-soluble granules) in stable aqueous active agent
preparations and moreover do not give off dust. The solid plant
protection compositions thus obtained are stable on storage.
[0376] An additional subject matter of the present invention is
accordingly the pesticidal, in particular fungicidal, insecticidal
or herbicidal, treatment of plants and their habitats with a plant
protection composition according to the invention or the use of the
disclosed plant protection compositions for the pesticidal, in
particular fungicidal, insecticidal or herbicidal, treatment of
plants and their habitats.
[0377] For this, the solid plant protection compositions according
to the invention, before they are used, are generally converted by
the user, e.g. the farmer or gardener, in a way essentially known,
by dissolving, dispersing or emulsifying in water, to a
ready-for-application application form, e.g. treated to give a
spray mixture (tank mix method).
[0378] The spray mixture prepared can be applied in a generally
known way in the spray method, especially by spraying, for
instance, with a mobile spraying device from nozzles which
distribute as finely as possible. Furthermore, the usual devices
and working techniques for this are known to a person skilled in
the art.
[0379] According to a particular embodiment, the treatment of
plants and their habitats is accordingly carried out in the spray
method. In this context, it is preferable for the preparation of
the spray mixture to be applied to be carried out by dissolving,
dispersing or emulsifying and particularly preferable again for the
dissolving, dispersing or emulsifying to be carried out in the tank
mix method.
[0380] An additional subject matter of the present invention is a
spray mixture comprising a plant protection composition according
to the invention for the pesticidal treatment of plants.
[0381] In a particular embodiment of the invention, the spray
mixture comprises from 0.0001 to 10% by weight, preferably from
0.001 to 1% by weight and in particular from 0.01 to 0.5% by weight
of plant protection active agent. This corresponds to approximately
from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight and
in particular from 0.1 to 2% by weight of plant protection
composition according to the invention.
[0382] The present invention will now be more fully described using
the following examples, which are not to be regarded as
limiting.
REFERENCE EXAMPLES 1 TO 37
Polyalkoxylate-Comprising Solids
[0383] A series of polyalkoxylate-comprising solids was prepared
according to processes V1, V2, V3 or V4 and evaluated.
Process V1: Preparation by Means of Freeze Drying
[0384] The respective ingredients were treated with water and
dissolved in a 250 ml round-bottomed flask with stirring at RT or
with gentle heating at 50.degree. C. Subsequently, the
round-bottomed flask was placed in an acetone/dry ice bath and the
mixture was frozen at approximately from -70 to -78.degree. C. to
give a solid mass. Alternatively, liquid nitrogen or liquid air was
used for the freezing. The freezing generally lasted only a few
minutes.
[0385] The flask was then connected to a conventional freeze drying
apparatus. Depending on amount, the freeze drying process lasted up
to 48 hours, a partial vacuum of less than 0.5 mbar typically being
installed.
[0386] The residues were isolated from the flasks, i.e. generally
scraped out with a spatula, and subsequently evaluated in their
properties.
Process V2: Preparation by Means of Evaporation
[0387] The ingredients are dissolved in water and a portion of this
amount is placed in a petri dish in a layer depth of ca. 1-2 mm.
The petri dish is, up to constant weight, placed on a hot plate and
the aqueous mixture is dried at 100.degree. C. by free evaporation
of water at atmospheric pressure.
Process V3: Preparation by Means of Rotary Evaporation
[0388] The ingredients are dissolved in water and evaporated on a
rotary evaporator at 60.degree. C. and 100 down to ca. 50 mbar.
[0389] The details with regard to ingredients, amounts, preparation
process and evaluation for some formulations are collated in the
following table 1.
TABLE-US-00001 TABLE 1 Ref. Ingredients Ex. (proportions in g)
Aqueous mixture Process Consistency.sup.1) Hygroscopicity.sup.2) 1a
(60) Urea 400 g.sup.3) V1 S-3 (40) W. LF 700 1b (50) W. LF 700 150
g.sup.3) V1 S-1 10.7% (65%) (50) Wettol D 1 1c (10) Urea 150
g.sup.3) V1 S-1 7.1% (65%) (40) Wettol D 1 (50) W. LF 700 2 (3) W.
LF 700 100 g.sup.3) V1 S-3 (4) Adinol OT (3) Urea 3 (5) W. LF 700
100 g.sup.3) V1 S-2 (1) Wettol D 1 (4) Urea 4 (5) W. LF 700 100
g.sup.3) V1 S-0/S-1 (2) Wettol D 1 (3) Urea 5 (2.1) W. LF 700 100
g.sup.3) V1 S-1 31.6% (65%) (2.9) Adinol OT (5) Urea 6 (5) W. LF
700 100 g.sup.3) V1 S-1 8.24% (65%) (2) Tamol NH 7519 (3) Urea 7
(50) W. LF 700 100 g.sup.3) V1 S-3 2.94% (65%) (20) Sipernat 22
(30) Urea 8 (50%) Wettol D 1 50 g/150 g.sup.4) V1 S-0 to (45%) W.
LF 700 S-1 (5%) Sipernat 50 S 9 (50%) Wettol D 1 50 g/150 g.sup.4)
V1 S-0 to 7.4% (65%) (40%) W. LF 700 S-1 (10%) Sipernat 50S 10
(45%) Wettol D 1 50 g/150 ml.sup.4) V1 S-1 (35%) W. LF 700 (20%)
Sipernat 50S 11 (50%) W. LF 700 20 g/80 ml.sup.4) V1 S-0 to 9.84%
(65%) (50%) Tamol NH7519 S-1 12 (50%) W. LF 700 20 g/80 ml.sup.4)
V1 S-0 to 12.81% (65%) (50%) Ufoxane 3 A S-1 (Starting solution
somewhat hazy) 13a (10 g) W. LF 700 20 g/80 ml.sup.4) V1 S-0 6.6%
(50%) (6.6 g) Ufoxane 3 A (3.3 g) Tamol NH 7519 13b (6 g) W. LF 700
In 80 ml.sup.5) V1 S-1 (6.7 g) Ufoxane 3 A (3.3 g) Tamol NH7519
(4.0 g) Aerosol OTA 14a (5 g) W. LF 700 In 80 ml.sup.5) V1 S-0 7.5%
(50%) (5 g) Klearfax AA 270 (10 g) Wettol D 1 14b (8 g) W. LF 700
In 80 ml.sup.5) V1 S-0 to (2 g) Pluronic PE 6800 S-1 (3.33 g) Tamol
NH7519 (6.66 g) Ufoxane 3 A 15 (50%) W. LF 700 20 g/160 ml.sup.4)
V1 S-4 (50%) Lutensit A-LBN 16 (40%) W. LF 700 In 80 ml.sup.5) V1
S-3 (10%) Ammonium sulfate (50%) Urea 17 (10 g) Tamol NH 7519 20
g/180 g.sup.4) V2 S-4 (10 g) W. LF 700 18 (10 g) Tamol NH 7519 20
g/180 g.sup.4) V3 S-4 (10 g) W. LF 700 19 (50%) Wettol D 1 20 g/80
ml.sup.4) V1 S-1-S-2 4.5% (50%) (50%) Cremophor EL 7.7% (65%) 20
(33.3%) Ufoxane 3A 20 g/80 ml.sup.4) V1 S-1 7.3% (50%) (50%)
Cremophor EL 13.2% (65%) (16.7%) Tamol NH 7519 21 (50%) Wettol D 1
20 g/80 ml.sup.4) V1 S-1 to 4.0% (50%) (50%) Lutensol AO3 S-2 7.0%
(65%) 22 (33.3%) Ufoxane 3A 20 g/80 ml.sup.4) V1 S-0 7.1% (50%)
(50%) Lutensol AO3 13.1% (65%) (16.7%) Tamol NH 7519 23 (6.7 g)
Ufoxane 3A 20 g/80 ml.sup.4) V1 S-0 7.5% (50%) (4.5 g) Synperonic
10/7 13.9% (65%) (5.5 g) Synperonic 10/11 (3.3 g) Tamol NH 7519 24
(10 g) Wettol D 1 20 g/80 ml.sup.4) V1 S-1 4.3% (50%) (4.5 g)
Synperonic 10/7 7.9% (65%) (5.5 g) Synperonic 10/11 25 (50 g)
Lutensol TO8 20 g/80 ml.sup.4) V1 S-1 to 4.6% (50%) (50 g) Wettol D
1 S-2 8.2% (65%) 26 (50 g) Lutensol ON 30 20 g/80 ml.sup.4) V1 S-1
4.3% (50%) (50 g) Wettol D 1 8.0% (65%) 27 (50 g) Lutensol ON 30 20
g/80 ml.sup.4) V1 S-0 7.5% (50%) (33.3 g) Ufoxane 3A 14.1% (65%)
(16.7 g) Tamol NH 7519 28 (50 g) Lutensol A 8 20 g/80 ml.sup.4) V1
S-0 4.6% (50%) (50 g) Wettol D 1 8.0% (65%) 29a (50 g) Lutensol A 8
20 g/80 ml.sup.4) V1 S-0 7.2% (50%) (33.3 g) Ufoxane 3A 13.5% (65%)
(16.7 g) Tamol NH 7519 29b (50 g) Lutensol AO 10 20 g/80 ml.sup.4)
V1 S-1 7.6% (50%) (33.3 g) Ufoxane 3A 13.8% (65%) (16.7 g) Tamol NH
7519 30 (50 g) Glycerox HE 20 g/80 ml.sup.4) V1 S-0 4.2% (50%) (50
g) Wettol D 1 7.8% (65%) 31 (50 g) Glycerox HE 20 g/80 ml.sup.4) V1
S-0 7.5% (50%) (33.3 g) Ufoxane 3A 14.2% (65%) (16.7 g) Tamol NH
7519 32 (50 g) Castor oil-20 EO 20 g/80 ml.sup.4) V1 S-1 (50 g)
Wettol D 1 .sup.1)Evaluations of the consistency: S-0: good
properties, solid powder which, on scratching or rubbing with a
spatula, remains solid and friable and shows no tendency to smear.
S-1: shows virtually no smearing on scratching with the spatula;
S-2: shows very slight smearing on scratching with the spatula;
S-3: clearly shows smearing under mechanical stress or on
scratching; S-4: the freeze-dried mass is already viscous and shows
considerable smearing; .sup.2)Hygroscopicity given in % by weight
of moisture absorption at a relative humidity value of 50% or 65%
(the determination was carried out in each case up to the
saturation value, i.e. constant weight, the increase in weight of 1
g samples in small petri dishes being determined up to 4 weeks)
.sup.3)Total amount of the ingredients dissolved in water
.sup.4)Amount of ingredient/amount of water .sup.5)Amount of water
in which the ingredients were dissolved
Process A4: Preparation by Means of Spray Drying
[0390] The ingredients were dissolved in water and spray dried in a
spray tower from Niro-Reiholb (disk tower; height: 6 m; diameter: 1
m; two-fluid nozzle with circulating gas unit, cyclone and filter
system; use of nitrogen; nozzle gas mass flow rate: 11.5 kg/h;
nozzle gas admission pressure: 2.7 bar; product inlet temperature:
20.degree. C.) under the conditions mentioned in the following
table 2.
TABLE-US-00002 TABLE 2 Gas mass Throughput Gas inlet Gas outlet
flow rate (kg/h) (spray Ex. Batch/Components temp. (.degree. C.)
temp. (.degree. C.) (kg/h) amount) 33 200 kg Water 162 79 460 22 50
kg Wettol D 1 50 kg Wettol LF 700 34 60 kg Water 162 84 490 19 15
kg Wettol D 1 10 kg Wettol LF 700 35***.sup.) 30 kg Water 154 84
500 18 20 kg Tamol NLP 10 kg Wettol LF 700 36 40 kg Water 162 83
510 20 10 kg Ufoxane 3A 10 kg Wettol LF 700 37 40 kg Water 123 77
500 12 10 kg Tamol NH 7519 10 kg Wettol LF 700 ***.sup.)Invalid
test; no discharge of product; ca. 50 kg of powder in the
filter.
[0391] The residual moisture contents of the solid formulations
obtained were 2.1% (example 33), 1.7% (example 34) or 1.5% (example
36).
[0392] The following table 3 is a digest of the ingredients
used.
TABLE-US-00003 TABLE 3 Name Correspondence Additional description
Manufacturer Wettol D 1 Sulfonate of the Sodium salt, cf. EP 707
445 BASF AG formula III Wettol LF 700 Alkoxylate of the
C.sub.12-C.sub.14-fatty alcohol .times. BASF AG formula I PO/EO,
cf. EP 707 445; Sipernat 22 Inorganic solid Silicon dioxide product
Degussa Sipernat 50S Inorganic solid Silicon dioxide product
Degussa Tamol NH 7519 Sulfonate of the Naphthalenesulfonic acid-
BASF AG formula II formaldehyde polycondensate, sodium salt Ufoxane
3A Sulfonate Lignosulfonate Lutensit A-LBN --
Dodecylbenzenesulfonic BASF AG acid, sodium salt Aerosol OTA
Additional auxiliary Cremophor EL Alkoxylate of the Polyglycol
ricinoleate BASF AG formula I Tamol NLP* Sulfonate of the
Naphthalenesulfonic acid- BASF AG formula II formaldehyde
polycondensate, ammonium salt Silicon SRE Additional auxiliary
Antifoaming agent Wacker Lutensol AO3 Alkoxylate of the
C.sub.13-C.sub.15-fatty alcohol .times. EO BASF AG formula I
Klearfax AA 270 Alkoxylate of the Phosphate ester of a BASF Corp.,
formula I polyalkoxylated fatty alcohol; US CAS No.: 68649-29-6
Pluronic PE 6800 -- PO/EO block polymer BASF AG Synperonic 10/7
Alkoxylate of the Fatty alcohol-EO Uniqema formula I Synperonic
10/11 Alkoxylate of the Fatty alcohol .times. EO Uniqema formula I
Lutensol TO8 Alkoxylate of the Iso-C.sub.13-alcohol .times. EO BASF
AG formula I Lutensol ON 30 Alkoxylate of the Iso-C.sub.10-Alkohol
.times. EO BASF AG formula I Lutensol A 8 Alkoxylate of the
C.sub.12-C.sub.14-Alcohol .times. EO BASF AG formula I Lutensol AO
10 Alkoxylate of the C.sub.13-C.sub.15-Alcohol .times. EO BASF AG
formula I Castor oil-20 EO Alkoxylate of the Castor oil .times. 20
EO formula I Glycerox HE Alkoxylate of the Ethoxylated glyceryl
cocoate; Croda Ltd., formula I commercial product with the GB CAS
No. 68553-03-7
[0393] Without being committed to the theory, the following
mechanism is proposed to explain the observation that relatively
high molecular weight sulfonates with high and, as a percentage by
weight, identical or similar proportions of polyalkoxylates produce
solid powders on spray drying or on freeze drying;
[0394] In both cases, both in spray drying and in freeze drying,
the solvent, generally water, is quickly and/or relatively gently
removed from the preconcentrates. In this context, it can be
assumed that, first, associates are present or are formed,
characterized in that, in addition to dipole-dipole and Van der
Waals interactions, "template" effects (i.e., favoring and/or
changing the incorporation of macromolecules in preformed
supermolecular aggregations as a result of cooperative effects,
similar to the processes known in the formation of many biological
macromolecular structures) also play a role, in which the cation of
the sulfonate interacts with the polyalkoxylate chain with
formation of chelate-like structures. In this way, poly- or
macromeric cations and poly- or macromeric anions with
comparatively high stability are produced.
[0395] It is known in general that large and/or macromeric unstable
anions with many degrees of freedom of the orientation in space,
i.e. low rigidity of the molecule, can in many cases form stable
lattices or solids with crystalline structure and/or associates
with melting points of greater than 50.degree. C. only with
likewise large and/or macromeric cations. On microscopic
inspection, these backbone associates survive on fast or gentle,
kinetically controlled removal of solvent according to the
invention. Macroscopically, this operation in the end produces
loose powders or granules, typically with proportions of air of at
least 20% by volume and bulk densities between 0.3 and 0.9
g/ml.
[0396] In contrast to this, the slow or nongentle removal of the
solvent from mixtures according to the invention, as takes place,
e.g., in a rotary evaporator, leads, with disintegration of the
molecular associates under thermodynamic control, to films or to
pasty masses of higher density (>0.9 g/ml) which are less
suitable for the preparation of plant protection granules.
[0397] The proposed mechanism is depicted simply to explain the
invention and does not limit it.
EXAMPLES 1 AND 2
Plant Protection Compositions Based on Epoxiconazole
[0398] Two plant protection compositions based on an epoxiconazole
suspension concentrate (epoxiconazole SC) were prepared according
to process V4 or V5 and evaluated.
Epoxiconazole SC:
[0399] 1.5 kg of SC were prepared according to EP 707 445 B1 by
milling, in a laboratory bead mill, an aqueous mixture with 12.5%
of epoxiconazole, 5% of Wettol LF 700, 2.5% of Tamol NH 7519 and
0.1% of Silicon SRE (antifoaming agent), a particle size
distribution of 80%<2 .mu.m being obtained.
EXAMPLE 1
[0400] The ingredients were dissolved in water and spray dried
according to process V4.
TABLE-US-00004 Gas mass Throughput Gas inlet Gas outlet flow rate
(kg/h) (spray Ex. Batch/Components temp. (.degree. C.) temp.
(.degree. C.) (kg/h) amount) 1 60 kg Water 115 75 500 9 5.6 kg
Wettol D 1 5.6 kg Wettol LF 700 4 kg Epoxiconazole SC
EXAMPLE 2
Process V5
Preparation by Means of a Fluidized Bed
[0401] An FBG laboratory unit (Turbojet model) from Huttlin is
fluidized at 70.degree. C. with ca. 80 m.sup.3 of nitrogen stream
with 1.5 kg of the mixture from example 33. 2.5 kg of epoxiconazole
SC are then sprayed on within 45 minutes via the three bottom
nozzles of the unit, a coarse-grained granule with good dispersing
properties being obtained. The granule output, calculated at 2.0
kg, was actually ca. 1.9 kg, with a proportion of active agent of
approximately 19% of epoxiconazole and a proportion of
polyalkoxylate (Wettol LF 700) of 38%.
[0402] The plant protection compositions according to the invention
are dust-free, quickly wettable, readily dispersible and
nonhygroscopic or only slightly hygroscopic granules with good
storage stability.
* * * * *